Determining surface wetting of metal with changing well fluids

ABSTRACT

Methods and apparatuses for determining surface wetting of a metallic material with changing well fluids. In general, the methods according to the invention include measuring electrical impedance spectroscopy (“EIS”) for a system simulating downhole conditions for the wetting of a surface. Methods and apparatuses for making EIS measurements model double-layer capacitance at a downhole surface in a well, from which the nature and quantification of the wetting of the surface can be inferred.

CROSS-REFERENCE TO RELATED APPLICATIONS

Not applicable.

TECHNICAL FIELD

The inventions are in the field of producing crude oil or natural gasfrom subterranean formations. More specifically, the inventionsgenerally relate to methods and apparatuses for determining surfacewetting with changing of well fluids. Applications of the methods andapparatuses include without limitation, for example, the designing ofspacer or inverter fluids and the field-operational parameters forwellbore cleanout and fluid separation prior to cementing operations ina well.

BACKGROUND ART

To produce oil or gas, a well is drilled into a subterranean formationthat is an oil or gas reservoir.

Well Servicing and Well Fluids

Generally, well services include a wide variety of operations that maybe performed in oil, gas, geothermal, or water wells, such as drilling,cementing, completion, and intervention. Well services are designed tofacilitate or enhance the production of desirable fluids such as oil orgas from or through a subterranean formation. A well service usuallyinvolves introducing a well fluid into a well.

Drilling is the process of drilling the wellbore. After a portion of thewellbore is drilled, sections of steel pipe, referred to as casing,which are slightly smaller in diameter than the borehole, are placed inat least the uppermost portions of the wellbore. The casing providesstructural integrity to the newly drilled borehole.

Cementing is a common well operation. For example, hydraulic cementcompositions can be used in cementing operations in which a string ofpipe, such as casing or liner, is cemented in a wellbore. The cementstabilizes the pipe in the wellbore and prevents undesirable migrationof fluids along the annulus between the wellbore and the outside of thecasing or liner from one zone along the wellbore to the next. Where thewellbore penetrates into a hydrocarbon-bearing zone of a subterraneanformation, the casing can later be perforated to allow fluidcommunication between the zone and the wellbore. The cemented casingalso enables subsequent or remedial separation or isolation of one ormore production zones of the wellbore, for example, by using downholetools such as packers or plugs, or by using other techniques, such asforming sand plugs or placing cement in the perforations. Hydrauliccement compositions can also be utilized in intervention operations,such as in plugging highly permeable zones or fractures in zones thatmay be producing too much water, plugging cracks or holes in pipestrings, and the like.

Completion is the process of making a well ready for production orinjection. This principally involves preparing a zone of the wellbore tothe required specifications, running in the production tubing andassociated downhole equipment, as well as perforating and stimulating asrequired.

Intervention is any operation carried out on a well during or at the endof its productive life that alters the state of the well or wellgeometry, provides well diagnostics, or manages the production of thewell. Workover can broadly refer to any kind of well intervention thatinvolves invasive techniques, such as wireline, coiled tubing, orsnubbing. More specifically, however, workover usually refers to aprocess of pulling and replacing a completion.

Drilling and Drilling Fluids

The well is created by drilling a hole into the earth (or seabed) with adrilling rig that rotates a drill string with a drilling bit attached tothe downward end. Usually the borehole is anywhere between about 5inches (13 cm) to about 36 inches (91 cm) in diameter. As upper portionsare cased or lined, progressively smaller drilling strings and bits mustbe used to pass through the uphole casings or liners, which steps theborehole down to progressively smaller diameters.

While drilling an oil or gas well, a drilling fluid is circulateddownhole through a drillpipe to a drill bit at the downhole end, outthrough the drill bit into the wellbore, and then back uphole to thesurface through the annular path between the tubular drillpipe and theborehole. The purpose of the drilling fluid is to maintain hydrostaticpressure in the wellbore, lubricate the drill string, and carry rockcuttings out from the wellbore.

The drilling fluid can be water-based or oil-based. Oil-based fluidstend to have better lubricating properties than water-based fluids,nevertheless, other factors can mitigate in favor of using a water-baseddrilling fluid. Such factors may include but not limited to presence ofwater-swellable formations, need for a thin but a strong and impermeablefiltercake, temperature stability, corrosion resistance, stuck pipeprevention, contamination resistance and production protection.

Cementing and Hydraulic Cement Compositions

Hydraulic cement is a material that when mixed with water hardens orsets over time because of a chemical reaction with the water. The cementcomposition sets by a hydration process, passing through a gel phase tosolid phase. Because this is a chemical reaction with water, hydrauliccement is capable of setting even under water.

The hydraulic cement, water, and any other components are mixed to forma hydraulic cement composition in fluid form. The hydraulic cementcomposition is pumped as a fluid (typically in the form of suspension orslurry) into a desired location in the wellbore. For example, incementing a casing or liner, the hydraulic cement composition is pumpedinto the annular space between the exterior surfaces of a pipe stringand the borehole (that is, the wall of the wellbore). The hydrauliccement composition should be a fluid for a sufficient time beforesetting to allow for pumping the composition into the wellbore and forplacement in a desired downhole location in the well. The cementcomposition is allowed time to set in the annular space, thereby formingan annular sheath of hardened, substantially impermeable cement. Thehardened cement supports and positions the pipe string in the wellboreand fills the annular space between the exterior surfaces of the pipestring and the borehole of the wellbore.

Wettability and Wetting of Solid Surfaces

The wettability of a solid surface or a film on a solid surface canimpact various well applications. For example, an oleaginous film on ametal surface of a tubular or a rock material of a subterraneanformation can affect bonding of hydraulic cement to the surface. Thewettability of rock or the wetting of the rock can affect the flow of afluid through the matrix of rock of a subterranean formation.

Wettability involves the contact between a liquid and a solid surface,resulting from the intermolecular interactions when the two differentphases are brought together. In general, the degree of wetting(wettability) is depends on a force balance between adhesive forcesbetween the liquid and solid surface and cohesive forces of the liquid(i.e., surface tensions). Adhesive forces between a liquid and solidcause a liquid drop to spread across the surface. Cohesive forces withinthe liquid cause the drop to ball up and avoid contact with the surface.

A measurement of the degree of wettability is the contact angle, theangle at which the liquid interface meets the dry solid interface. Ifthe wettability is very favorable to the liquid, the contact angle willbe low, and the fluid will spread to cover or “wet” a larger area of thesolid surface. If the wettability is unfavorable, the contact angle willbe high, and the fluid will form a compact, self-contained droplet onthe solid surface. If the contact angle of a water droplet on a solidsurface is less than 90°, the surface may be said to be “water-wettable”(and inverse proportionally, probably not oil-wettable); whereas if thecontact angle of an oil droplet on a solid surface is less than 90°, thesurface may be said to be “oil-wettable” (and inverse proportionally,not water-wettable. The surfaces of some materials are both waterwettable and oil wettable.

TABLE 1 Surface Adhesion of Tension of the liquid to a liquid solidsurface Contact Angle Degree of Wettability Weak Strong θ = 0° Theoretically perfectly wettable Strong Strong 0° < θ < 90° Highwettability Weak Weak 0° < θ < 90° High wettability Strong Weak 90° ≦ θ< 180°  Low wettability Strong Weak θ = 180° Theoretically perfectlynon-wettable

As used herein, a wet or wetted surface or the wetting of a surface mayrefer to a liquid phase that is directly in contact with and adhered tothe surface of a solid body. For example, the liquid phase can be anoleaginous film on the surface of a metallic tubular or the face of aborehole in the material of a subterranean formation.

Some well fluids can form such a film or layer on a downhole surface,which can have undesirable effects. The fluid (or a liquid component ofthe fluid) can form a film or layer on the surface, which can act as aphysical barrier between the material of the underlying solid body and afluid adjacent to the surface of the solid body. In effect, such a filmpresents a different wettability characteristic than the material of theunderlying solid body. For example, an oleaginous film on the surface ofa metal tubular blocks water from wetting the underlying surface, whichwould otherwise be water-wettable.

A metallic surface of a downhole tubular is typically both waterwettable and oil wettable. If first wetted with an oleaginous film,however, the oleaginous film on the metallic surface blocks the metalsurface from being wettable with a water-based fluid.

Wetting of Tubulars and Formation Surfaces for Cementing

Hydraulic cement compositions do not bond well to oil-wetted surfaces.After drilling a wellbore with an oil-based drilling mud, the surfacesof tubulars and the formation in the wellbore may become oil-wetted withan oleaginous film. It is necessary to remove the film on the solidsurface of the tubular from being oil-wetted with such a film to improvecement bonding.

In a case where complete surface wetting with water is not achievedprior to placing cement in the desired zone of interest, only partialbonding of the surfaces with cement is obtained. Because of thisincomplete surface bonding, there is a proportional decrease in theshear bond strength of the interface between the set cement sheath andthe formation/tubular surfaces and premature interfacial de-bondingmight occur under the loads experienced during the course of the welloperations. This may have unwanted consequences such as interzonalcommunication, loss of production, and sustained casing pressure. Any ofthese can be detrimental to the safety and economics of hydrocarbonproduction from the well.

Significance of Interfacial Phenomena

Physical, chemical, and electrical properties of matter confined tophase boundaries are often profoundly different from those of the samematter in bulk. For many systems, although multiphase, the fraction oftotal mass localized at the phase boundaries is small that thecontribution of such boundary properties to the general systemproperties is negligible.

However, many important systems exist under which these properties playsignificant role. For example, such systems include dispersions inliquids, which can be of solids (e.g., sols, suspensions, or slurries)or of other liquids (e.g., emulsions). In dispersions, the phaseboundary area is so large relative to the volume of the system that asubstantial fraction of the total mass of the system is present at theboundaries. Surfactants (also known as surface-active agents) play amajor role in these systems.

Another such system is where the phenomena occurring at the phaseboundaries are so different from the bulk phases that the behavior ofthe system is substantially determined by phase-boundary processes.Examples include detergency, floatation, and cleanout.

It is necessary to understand the causes of the behavior of matter atthe phase-interfaces and the variables that affect this behavior inorder to predict and control the properties of systems in whichphase-boundary properties play a significant role. In addition, astemperature, pressure, shear, and other conditions vary, theseproperties used to quantify interfacial phenomena will also change. Thesystems of well fluids and operations with well fluids can be highlycomplex and difficult to predict.

It would be highly desirable in well operations to have methods fordetermining wettability and improving operating conditions and contacttimes for well fluids. Applications include, for example, the designingof spacer or inverter fluids and determining the field-operationalparameters for wellbore cleanout and fluid separation prior to cementingoperations in a well.

SUMMARY OF THE INVENTION

According to the invention, methods and apparatuses are provided fordetermining surface wetting with changing of well fluids. In general,the methods according to the invention include measuring electricalimpedance spectroscopy (“EIS”) for a system simulating downholeconditions for the wetting of a surface. Methods and apparatuses formaking EIS measurements model double-layer capacitance at a downholesurface in a well under the conditions in the well, from which thenature and quantification of the wetting of the surface for suchconditions can be inferred.

In addition, methods are provided for making EIS measurements downholein a well to measure surface wetting directly in the downholeenvironment and conditions.

These and other aspects of the invention will be apparent to one skilledin the art upon reading the following detailed description. While theinvention is susceptible to various modifications and alternative forms,specific embodiments thereof will be described in detail and shown byway of example. It should be understood, however, that it is notintended to limit the invention to the particular forms disclosed, but,on the contrary, the invention is to cover all modifications andalternatives falling within the spirit and scope of the invention asexpressed in the appended claims.

BRIEF DESCRIPTION OF THE DRAWING

The accompanying drawing is incorporated into the specification to helpillustrate examples according to the presently most-preferred embodimentof the invention.

FIGS. 1 a, 1 b, and 1 c are illustrations of a sequence of fluiddisplacement in a wellbore during a cementing operation. The spacerfluid is illustrated being pumped into a wellbore of a well penetratinga formation 10 and down through a casing (which has not yet beencemented) and then out the lower end of the casing and up through theannulus between the outside of the casing and the borehole of thewellbore. FIG. 1 a illustrates a drilling mud initially the annulus ofthe wellbore around the casing. FIG. 1 b illustrates a spacer fluidbeing pumped through the casing to displace the drilling mud from theannulus. FIG. 1 c illustrates a cement composition (sometimes referredto as a cement slurry) being pumped through the casing to displace thespacer fluid and placed in the annulus for cementing the casing in thewellbore. To seal the annulus with cement requires good cement bondingbetween both the outer wall of the casing and the rock of thesubterranean formation of the borehole.

FIG. 2 is an illustration modeling fluid intermixing between a priordrilling mud in a wellbore and a spacer fluid as the spacer fluiddisplaces the prior well fluid, which is similar to the stageillustrated in FIG. 1 b. In FIG. 2, the spacer fluid is illustratedbeing pumped into the well and down through a casing (which has not yetbeen cemented) and then out the lower end of the casing and up throughthe annulus between the outside of the casing and the borehole of thewellbore. As the spacer fluid displaces the prior fluid in the wellbore,there is a diffused layer of mixing and channeling between the priorfluid and the spacer fluid. The diffused layer includes varying mixturesof the prior fluid in the well and spacer fluid. Such a diffused layeris sometimes referred to as contaminated spacer fluid. The spacer fluidbeing pumped behind the diffused layer is sometimes referred to as pureor uncontaminated spacer fluid.

FIG. 3 is a graphical representation of a diffused layer between anoil-based drilling mud and a water-based spacer fluid, wherein at somedegree of mixing and depending on the particular compositions of theoil-based and water-based fluids, the continuous phase of the fluid inthe zone of the well inverts from oil-based to water-based.

FIG. 4 illustrates the formation of an electrical double layer at theinterface between a positively charged surface and a bulk liquidincluding electrolyte ions, without any intervening film of anoleaginous liquid phase on the positively charged surface.

FIG. 5 is a graphical illustration of electric potential distribution ofan electrical double layer as a function of the dielectric dipole moment(i.e., Debye length) of the molecules of a liquid phase, includingshowing the region of the slipping plane.

FIG. 6 a is a vertical cross-sectional view of an electrical apparatusfor measuring the change in surface wetting on a metal surface, whichcan be selected, for example, to simulate a metal surface in a well. Theelectrical circuit for measuring electrical impedance between theelectrodes of the apparatus is not shown in detail. FIG. 6 b is a topview of the apparatus in FIG. 6 a, illustrating the insulated separationof the electrodes in the container wall of the apparatus. This type ofapparatus can measure the change in surface wetting on an electrodesurface from a first liquid phase to a second liquid phase as a secondbulk fluid including the second liquid phase is sheared in the containerof the apparatus at a controlled rate for a controlled contact time. Theelectrode surfaces can simulate the metallic body of a tubular. Thefirst liquid phase can simulate a prior oleaginous film formed on thesurface. The second bulk fluid can and conditions of shear and time cansimulate the displacement of the oleaginous film by a spacer fluid.

FIG. 7 a is a vertical cross-sectional view of an electrical apparatusfor measuring the change in surface wetting on a dielectric solidsurface, which can be selected, for example, to simulate a rock surfaceof a subterranean formation. The electrical circuit for measuringelectrical impedance between the electrodes of the apparatus is notshown in detail. FIG. 7 b is a top view of the apparatus in FIG. 7 a,illustrating the insulated separation of the dielectric surfaces in thecontainer wall of the apparatus. It should be understood, of course,that the dielectric constant of the insulating material of the containershould be lower than that of any liquid phases being tested for wettingon the testing surface. Similarly, it should be understood, of course,that the dielectric constant of the insulating material of the containershould be lower than that of the material of the testing surface. Afirst electrode is placed in electrical contact with the dielectricsolid to be tested. This type of apparatus can measure the change insurface wetting on a tested dielectric surface from a first liquid phaseto a second liquid phase as a second bulk fluid including the secondliquid phase is sheared in the container of the apparatus at acontrolled rate for a controlled contact time. The dielectric solidsurfaces can be selected to simulate the rock of a subterraneanformation in a well. The first liquid phase can simulate a prioroleaginous film formed on the surface of the rock. The second bulk fluidcan and conditions of shear and time can simulate the displacement ofthe oleaginous film by a spacer fluid.

FIG. 8 is a vertical cross-sectional view of an alternative electricalapparatus for measuring the change in surface wetting on a dielectricsolid surface, which can be selected, for example, to simulate a rocksurface of a subterranean formation. As illustrated in FIG. 8, in thisembodiment the rock surface is axially separated from another electrodeexposed to a bulk fluid in the chamber of the container. It should beunderstood, of course, that the dielectric constant of the insulatingmaterial of the container should be higher than that of any liquidphases being tested for wetting on the testing surface. This type ofapparatus can measure the change in surface wetting on a testeddielectric surface from a first liquid phase to a second liquid phase asa second bulk fluid including the second liquid phase is sheared in thecontainer of the apparatus at a controlled rate for a controlled contacttime. The dielectric solid surfaces can be selected to simulate the rockof a subterranean formation in a well. The first liquid phase cansimulate a prior oleaginous film formed on the surface of the rock. Thesecond bulk fluid can and conditions of shear and time can simulate thedisplacement of the oleaginous film by a spacer fluid.

FIGS. 9 a and 9 b are vertical cross-sectional views illustrating anembodiment depicting direct electrical measurements in a well, which canbe used, for example, during the real-time pumping operations todetermine any change in wetting of a downhole tubular surface during awell operation such as cementing. FIG. 9 a is a vertical cross-sectionalview of a portion of a metallic tubular, such as a casing, positioned ina wellbore. FIG. 9 b is a detail view of a test probe device associatedwith a portion of the casing in the wellbore.

FIG. 10 is a graphical illustration representing voltage (V) and current(I) waveforms in time (t) in a pseudo-linear system, for which thecurrent response to a sinusoidal potential will be a similar sinusoidalsignal at the same frequency, but with a lag in phase.

FIG. 11 illustrates an example of a circuit that can be used forimpedance modeling in electrical systems. FIG. 11 is similar to the typeof circuit known as a Failed Paint Model (FP) circuit model.

FIG. 12 illustrates an example of a circuit that can be used forimpedance modeling in electrical systems. FIG. 12 is similar to the typeof circuit known as a Failed Paint Model with Diffusion (“CPED”) circuitmodel.

FIG. 13 shows an example of Nyquist plot comparing the impedance databefore and after surface wetting with a Failed Paint Model (FP) circuitmodel as in FIG. 11.

FIG. 14 shows an example of a Bode plot comparing the impedance databefore and after surface wetting with a Failed Paint Model (FP) circuitmodel as in FIG. 11.

FIG. 15 shows an example of a Nyquist plot comparing the impedance databefore and after surface wetting using a Constant Phase Element withDiffusion (“CPED”) circuit model as in FIG. 12.

FIG. 16 shows an example of a Nyquist plot from Electrical ImpedanceSpectroscopy under a no shear condition for different percentage extentsof non-aqueous liquid phase coverage, where the non-aqueous film used isan Oil Based Mud (“OBM”) made with mineral oil and the electrolyte usedis a water-based inverter fluid.

FIG. 17 shows an example of a Bode plot of impedance vs. frequency,before and after surface wetting using a Constant Phase Element withDiffusion (“CPED”) circuit model as in FIG. 12.

FIG. 18 shows a Bode magnitude plot from Electrical ImpedanceSpectroscopy for different extents of non-aqueous film coveragecorresponding to the Nyquist plot in FIG. 16.

FIG. 19 is a graph of double layer capacitance vs. non-oil-wetting filmcoverage for a grease and salt-water combination.

FIG. 20 is a graph of double layer capacitance vs. non-oil-wetting filmcoverage for OBM and salt-water combination.

FIG. 21 is a graph of inferred double-layer capacitance vs. percentcoverage of several different combinations of non-aqueous films inwater-based bulk fluids from electrical measurements in an electricalcell using an identical first electrode and second electrode.

FIG. 22 shows Bode magnitude plots at different durations of shear forthe measuring of the effect of contact time with 0.05 gal/bbl surfactantconcentration in an aqueous bulk spacer fluid, where the surfactant isan equiproportional mixture of surfactants including alcohol ethersulfate, a low hydrolipic balance non-ionic nonylphenol, and a highhydrolipic balance non-ionic nonylphenol, after following the steps of:(1) placing a spacer fluid in the test cell and taking EIS measurement;(2) starting from a state where the electrodes are coated withnon-aqueous film and the test cell is filled with the spacer fluid at noshear and taking EIS measurements; and (3) shear is applied by rotatinga cylindrical bob at 900 RPM in a configuration similar to as shown inFIGS. 6 a and 6 b and EIS data is recorded at intermittent times of 1minute increments from 1 minute to 7 minutes.

FIG. 23 shows Bode magnitude plots for the experiment in FIG. 22repeated with 0.1 gal/bbl surfactant concentration.

FIG. 24 shows Bode magnitude plots for Experiment in FIG. 22 repeatedwith 0.2 gal/bbl surfactant concentration, at intermittent times of1-minute increments from 1 minute to 3 minutes.

FIG. 25 shows experimental Bode magnitude plots showing the effect ofshear rates after following the steps of: (1) placing pure spacer fluidin the test cell and taking EIS measurement; (2) starting from a statewhere the electrodes are coated with non-aqueous film and the test cellis filled with the spacer fluid at no shear and taking EIS measurements;and (3) shear is applied by rotating a cylindrical bob for 60 seconds atdifferent RPMs of 900 RPM, 1200 RPM, and 1250 RPM in a configurationsimilar to the apparatus illustrated in FIGS. 6 a and 6 b and EIS datais recorded at 1 minute.

DETAILED DESCRIPTION OF PRESENTLY PREFERRED EMBODIMENTS AND BEST MODEDefinitions and Usages

Interpretation

The words or terms used herein have their plain, ordinary meaning in thefield of this disclosure, except to the extent explicitly and clearlydefined in this disclosure or unless the specific context otherwiserequires a different meaning.

If there is any conflict in the usages of a word or term in thisdisclosure and one or more patent(s) or other documents that may beincorporated by reference, the definitions that are consistent with thisspecification should be adopted.

The words “comprising,” “containing,” “including,” “having,” and allgrammatical variations thereof are intended to have an open,non-limiting meaning. For example, a composition comprising a componentdoes not exclude it from having additional components, an apparatuscomprising a part does not exclude it from having additional parts, anda method having a step does not exclude it having additional steps. Whensuch terms are used, the compositions, apparatuses, and methods that“consist essentially of” or “consist of” the specified components,parts, and steps are specifically included and disclosed.

The control or controlling of a condition includes any one or more ofmaintaining, applying, or varying of the condition. For example,controlling the temperature of a substance can include maintaining aninitial temperature, heating, or cooling.

The indefinite articles “a” or “an” mean one or more than one of thecomponent, part, or step that the article introduces.

Whenever a numerical range of degree or measurement with a lower limitand an upper limit is disclosed, any number and any range falling withinthe range is also intended to be specifically disclosed. For example,every range of values (in the form “from a to b,” or “from about a toabout b,” or “from about a to b,” “from approximately a to b,” and anysimilar expressions, where “a” and “b” represent numerical values ofdegree or measurement) is to be understood to set forth every number andrange encompassed within the broader range of values.

Terms such as “first,” “second,” “third,” etc. are assigned arbitrarilyand are merely intended to differentiate between two or more components,parts, or steps that are otherwise similar or corresponding in nature,structure, function, or action. For example, the words “first” and“second” serve no other purpose and are not part of the name ordescription of the following name or descriptive terms. The mere use ofthe term “first” does not require that there be any “second” similar orcorresponding component, part, or step. Similarly, the mere use of theword “second” does not require that there by any “first” or “third”similar or corresponding component, part, or step. Further, it is to beunderstood that the mere use of the term “first” does not require thatthe element or step be the very first in any sequence, but merely thatit is at least one of the elements or steps. Similarly, the mere use ofthe terms “first” and “second” does not necessarily require anysequence. Accordingly, the mere use of such terms does not excludeintervening elements or steps between the “first” and “second” elementsor steps, etc.

Well Terms

In the context of production from a well, oil and gas are understood torefer to crude oil and natural gas. Oil and gas are naturally occurringhydrocarbons in certain subterranean formations.

A “subterranean formation” is a body of rock that has sufficientlydistinctive characteristics and is sufficiently continuous forgeologists to describe, map, and name it.

In geology, rock or stone is a naturally occurring solid aggregate ofminerals or mineraloids. The Earth's outer solid layer, the lithosphere,is made of rock. Three majors groups of rocks are defined: igneous,sedimentary, and metamorphic.

A subterranean formation having a sufficient porosity and permeabilityto store and transmit fluids is sometimes referred to as a “reservoir.”The vast majority of reservoir rocks are sedimentary rocks, but highlyfractured igneous and metamorphic rocks sometimes contain substantialreservoirs as well.

A subterranean formation containing oil or gas may be located under landor under the seabed off shore. Oil and gas reservoirs are typicallylocated in the range of a few hundred feet (shallow reservoirs) to a fewtens of thousands of feet (ultra-deep reservoirs) below the surface ofthe land or seabed.

A “well” includes a wellhead and at least one wellbore from the wellheadpenetrating the earth. The “wellhead” is the surface termination of awellbore, which surface may be on land or on a seabed. A “well site” isthe geographical location of a wellhead of a well. It may includerelated facilities, such as a tank battery, separators, compressorstations, heating or other equipment, and fluid pits. If offshore, awell site can include a platform.

The “wellbore” refers to the drilled hole, including any cased oruncased portions of the well or any other tubulars in the well. The“borehole” usually refers to the inside wellbore wall, that is, the rocksurface or wall that bounds the drilled hole. A wellbore can haveportions that are vertical, horizontal, or anything in between, and itcan have portions that are straight, curved, or branched. As usedherein, “uphole,” “downhole,” and similar terms are relative to thedirection of the wellhead, regardless of whether a wellbore portion isvertical or horizontal.

A wellbore can be used as a production or injection wellbore. Aproduction wellbore is used to produce hydrocarbons from the reservoir.An injection wellbore is used to inject a fluid, e.g., liquid water orsteam, to drive oil or gas to a production wellbore.

As used herein, introducing “into a well” means introduced at least intoand through the wellhead. According to various techniques known in theart, tubulars, equipment, tools, or well fluids can be directed from thewellhead into any desired portion of the wellbore.

As used herein, the word “tubular” means any kind of body in the form ofa tube. Examples of tubulars include, but are not limited to, a drillpipe, a casing, a tubing string, a line pipe, and a transportation pipe.Tubulars can also be used to transport fluids into or out of asubterranean formation, such as oil, gas, water, liquefied methane,coolants, and heated fluids. For example, a tubular can be placedunderground to transport produced hydrocarbons or water from asubterranean formation to another location.

As used herein, the term “annulus” means the space between two generallycylindrical objects, one inside the other. The objects can be concentricor eccentric. Without limitation, one of the objects can be a tubularand the other object can be an enclosed conduit. The enclosed conduitcan be a wellbore or borehole or it can be another tubular. Thefollowing are some non-limiting examples illustrate some situations inwhich an annulus can exist. Referring to an oil, gas, or water well, inan open hole well, the space between the outside of a tubing string andthe borehole of the wellbore is an annulus. In a cased hole, the spacebetween the outside of the casing the borehole is an annulus. Inaddition, in a cased hole there may be an annulus between the outsidecylindrical portion of a tubular such as a production tubing string andthe inside cylindrical portion of the casing. An annulus can be a spacethrough which a fluid can flow or it can be filled with a material orobject that blocks fluid flow, such as a packing element. Unlessotherwise clear from the context, as used herein an annulus is a spacethrough which a fluid can flow.

As used herein, a “well fluid” broadly refers to any fluid adapted to beintroduced into a well for any purpose. A well fluid can be, forexample, a drilling fluid, a cement composition, a treatment fluid, or aspacer fluid. If a well fluid is to be used in a relatively smallvolume, for example less than about 200 barrels (32 m³), it is sometimesreferred to as a wash, dump, slug, or pill.

Drilling fluids, also known as drilling muds or simply “muds,” aretypically classified according to their base fluid (that is, thecontinuous phase). A water-based mud (“WBM”) has solid particulate(e.g., clays, bulk density increasing agents, lost circulationmaterials) suspended in an aqueous liquid as the continuous phase. Thewater can be brine. A brine-based drilling fluid is a water-based mud inwhich the aqueous component is brine. In some cases, oil may beemulsified in a water-based drilling mud. An oil-based mud (“OBM”) hassolid particulate suspended in oil as the continuous phase. In somecases, an aqueous phase of water or brine is emulsified in the oil.Drill Cuttings from the formation will be the additional solidparticulates getting suspended in both oil-based and water based muds asthe drilling process begins.

As used herein, the word “treatment” refers to any treatment forchanging a condition of any portion of a wellbore or an adjacentsubterranean formation; however, the word “treatment” does notnecessarily imply any particular treatment purpose. A treatment usuallyinvolves introducing a well fluid for the treatment, in which case itmay be referred to as a treatment fluid, into a well. As used herein, a“treatment fluid” is a fluid used in a treatment. The word “treatment”in the term “treatment fluid” does not necessarily imply any particulartreatment or action by the fluid.

As used herein, the terms spacer fluid, wash fluid, and inverter fluidcan be used interchangeably. A spacer fluid is a fluid used tophysically separate one special-purpose fluid from another. It may beundesirable for one special-purpose fluid to mix with another used inthe well, so a spacer fluid compatible with each is used between thetwo. A spacer fluid is usually used when changing between well fluidsused in a well.

For example, a spacer fluid is used to change from a drilling fluidduring drilling to cement composition during cementing operations in thewell. In case of an oil-based drilling fluid, it should be kept separatefrom a water-based cementing fluid. In changing to the latter fluid, achemically treated water-based spacer fluid is usually used to separatethe drilling fluid from the water-based cementing fluid.

A spacer fluid specially designed to separate a special purposeoil-external fluid from a special purpose water-external fluid may betermed as an inverter fluid. Inverter fluids may be so designed that thediffused contaminated layer between both the special purpose fluids hasprogressive variation in properties like solids carrying capability,electrical conductivity, rheology, and chemical potential. In otherwords, inverter fluids may be ideally designed to be fully compatiblephysically and chemically with either or both of the special purposefluids under the simulated conditions of pressure, temperature andshear. Compatibility may be warranted by rheological investigations orvisual observations at all intermediate compositions. Unwantedflocculation, coagulation, or excessive thinning of the admixturecompared to the original fluids is typically considered to be asignature for incompatibility.

In the context of cementing, compatibility can be determined bymonitoring viscosity upon mixing. For compatibility, the viscosity ofany mixture of two well fluids should be between the viscosity of eitherfluid. For example, the viscosity of an oil-based drilling mud may be,for example, about 100 cP. The viscosity of a spacer fluid may be, forexample, about 200 cP. These two well fluids would be consideredcompatible if the viscosity of any mixture of the two fluids is in therange of about 100 cP to about 200 cP; but if outside this viscosityrange, then a high degree of fingering, channeling, gelling, settling,separating, etc. would be likely to occur on mixing the two fluids. Theproper selection of well fluids must be used for a successful cementingoperation.

Volumes of spacer fluid that are consumed in channel lengths due tocontamination process are not sufficient to clean wellbore surfaces orchange wetting of a surface. These volumes should be consideredsacrificial and the amount of pure uncontaminated spacer is estimatedfrom surface wetting techniques.

A zone refers to an interval of rock along a wellbore that isdifferentiated from uphole and downhole zones based on hydrocarboncontent or other features, such as permeability, composition,perforations or other fluid communication with the wellbore, faults, orfractures. A zone of a wellbore that penetrates a hydrocarbon-bearingzone that is capable of producing hydrocarbon is referred to as a“production zone.” A “treatment zone” refers to an interval of rockalong a wellbore into which a well fluid is directed to flow from thewellbore. As used herein, “into a treatment zone” means into and throughthe wellhead and, additionally, through the wellbore and into thetreatment zone.

As used herein, a downhole fluid is an in-situ fluid in a well, whichmay be the same as a well fluid at the time it is introduced, or a wellfluid mixed with another fluid downhole, or a fluid in which chemicalreactions are occurring or have occurred in-situ downhole.

Generally, the greater the depth of the formation, the higher the statictemperature and pressure of the formation. Initially, the staticpressure equals the initial pressure in the formation before production.After production begins, the static pressure approaches the averagereservoir pressure.

A “design” refers to the estimate or measure of one or more parametersplanned or expected for a particular stage of a well service orassociated well fluid. For example, a fluid can be designed to havecomponents that provide a minimum viscosity for at least a specifiedtime under expected downhole conditions. A well service may includedesign parameters such as fluid volume to be pumped, required pumpingtime for a treatment, or the shear conditions of the pumping, andcontact time of a treatment fluid with a zone of interest.

The term “design temperature” refers to an estimate or measurement ofthe actual temperature at the downhole environment at the time of a welltreatment. That is, design temperature takes into account not only thebottom hole static temperature (“BHST”), but also the effect of thetemperature of the well fluid on the BHST during treatment. The designtemperature is sometimes referred to as the bottom hole circulationtemperature (“BHCT”). Because treatment fluids may be considerablycooler than BHST, the difference between the two temperatures can bequite large. Ultimately, if left undisturbed, a subterranean formationwill return to the BHST.

Substances and Chemicals

A substance can be a pure chemical or a mixture of two or more differentchemicals.

A pure chemical is a sample of matter that cannot be separated intosimpler components without chemical change. A chemical element iscomposed of atoms with identical atomic number. A chemical compound isformed from different elements chemically combined in definiteproportions by mass.

An atom or molecule is the smallest particle of a chemical that retainsthe chemical properties of the element or compound. A molecule is two ormore chemically bound atoms with characteristic composition andstructure. Making or breaking bonds in a molecule changes it to adifferent chemical.

An ionic compound is made of distinguishable ions, including at leastone cation (a positively charged ion) and at least one anion (anegatively charged ion), held together by electrostatic forces. An ionis an atom or molecule that has acquired a charge by either gaining orlosing electrons. An ion can be a single atom or molecular. An ion canbe separated from an ionic compound, for example, by dissolving the ionsof the compound in a polar solvent.

Physical States, Phases, and Materials

As used herein, “phase” is used to refer to a substance having achemical composition and physical state that is distinguishable from anadjacent phase of a substance having a different chemical composition ora different physical state.

The word “material” is often used as a synonym for a single phase of abulk scale (larger than a particle), although it can sometimes mean abulk scale of a mixture of phases, depending on the context.

As used herein, if not other otherwise specifically stated, the physicalstate or phase of a substance (or mixture of substances) and otherphysical properties are determined at a temperature of 77° F. (25° C.)and a pressure of 1 atmosphere (Standard Laboratory Conditions) withoutapplied shear.

Continuum Mechanics and Rheology

One of the purposes of identifying the physical state or phase of asubstance and measuring viscosity or other physical characteristics of afluid is to establish whether it is pumpable. In the context of oil andgas production, the pumpability of a fluid is with particular referenceto the ranges of physical conditions that may be encountered at awellhead and with the types and sizes of pumps available to be used forpumping fluids into a well. Another purpose is to determine what thephysical state of the substance and its physical properties will beduring pumping through a wellbore and under other downhole conditions inthe well, including over time and changing temperatures, pressures, andshear rates.

Continuum mechanics is a branch of mechanics that deals with theanalysis of the kinematics and the mechanical behavior of materialsmodeled as a continuous mass on a large scale rather than as distinctparticles. Fluid mechanics is a branch of continuum mechanics thatstudies the physics of continuous materials that take the shape of theircontainer. Rheology is the study of the flow of matter: primarily in theliquid state, but also as “soft solids” or solids under conditions inwhich they respond with plastic flow rather than deforming elasticallyin response to an applied force. It applies to substances that have acomplex structure, such as fluid suspensions, gels, etc. The flow ofsuch substances cannot be fully characterized by a single value ofviscosity, which varies with temperature, pressure, and other factors.For example, ketchup can have its viscosity reduced by shaking (or otherforms of mechanical agitation) but water cannot.

Particles, Particulates, Aggregates, and Fibers

As used herein, a “particle” refers to a body having a finite mass andsufficient cohesion such that it can be considered as an entity buthaving relatively small dimensions. A particle can be of any sizeranging from molecular scale to macroscopic, depending on context.

A particle can be in any physical state. For example, a particle of asubstance in a solid state can be as small as a few molecules on thescale of nanometers up to a large particle on the scale of a fewmillimeters, such as large grains of sand. Similarly, a particle of asubstance in a liquid state can be as small as a few molecules on thescale of nanometers or a large drop on the scale of a few millimeters.

As used herein, “particulate” or “particulate material” refers to matterin the physical form of distinct particles in a solid or liquid state(which means such an association of a few atoms or molecules). Aparticulate is a grouping of particles based on common characteristics,including chemical composition and particle size range, particle sizedistribution, or median particle size. As used herein, a particulate isa grouping of particles having similar chemical composition and particlesize ranges anywhere in the range of about 1 micrometer (e.g.,microscopic clay or silt particles) to about 3 millimeters (e.g., largegrains of sand).

As used herein, a particle can be an aggregate or a composite ofdifferent solid phases bound together.

It should be understood that the terms “particle” and “particulate,”includes all known shapes of particles including substantially rounded,spherical, oblong, ellipsoid, rod-like, fiber, polyhedral (such as cubicmaterials), etc., and mixtures thereof. For example, the term“particulate” as used herein is intended to include solid particleshaving the physical shape of platelets, shavings, flakes, ribbons, rods,strips, spheroids, toroids, pellets, tablets or any other physicalshape.

As used herein, a fiber is a particle or grouping of particles having anaspect ratio L/D greater than 5/1.

Dispersions

A dispersion is a system in which particles of a substance of onechemical composition and physical state are dispersed in anothersubstance of a different chemical composition or physical state. If asubstance has more than one phase, the most external phase is referredto as the continuous phase of the substance as a whole, regardless ofthe number of different internal phases or nested phases.

A dispersion can be classified a number of different ways, includingbased on the size of the dispersed particles, the uniformity or lack ofuniformity of the dispersion, and, if a fluid, whether or notprecipitation occurs.

Classification of Dispersions: Heterogeneous and Homogeneous

A dispersion is considered to be heterogeneous if the dispersedparticles are not dissolved and are greater than about 1 nanometer insize. (For reference, the diameter of a molecule of toluene is about 1nm).

Heterogeneous dispersions can have gas, liquid, or solid as an externalphase. For example, in a case where the dispersed-phase particles areliquid in an external phase that is another liquid, this kind ofheterogeneous dispersion is more particularly referred to as anemulsion. A solid dispersed phase in a continuous liquid phase isreferred to as a sol, suspension, or slurry, partly depending on thesize of the dispersed solid particulate.

A dispersion is considered to be homogeneous if the dispersed particlesare dissolved in solution or the particles are less than about 1nanometer in size. Even if not dissolved, a dispersion is considered tobe homogeneous if the dispersed particles are less than about 1nanometer in size.

Classification of Heterogeneous Dispersions: Suspensions and Colloids

Heterogeneous dispersions can be further classified based on thedispersed particle size.

A heterogeneous dispersion is a “suspension” where the dispersedparticles are larger than about 50 micrometer. Such particles can beseen with a microscope, or if larger than about 50 micrometers (0.05mm), with the unaided human eye. The dispersed particles of a suspensionin a liquid external phase may eventually separate on standing, e.g.,settle in cases where the particles have a higher density than theliquid phase. Suspensions having a liquid external phase are essentiallyunstable from a thermodynamic point of view; however, they can bekinetically stable over a long period depending on temperature and otherconditions.

A heterogeneous dispersion is a “colloid” where the dispersed particlesrange up to about 50 micrometer (50,000 nanometers) in size. Thedispersed particles of a colloid are so small that they settle extremelyslowly, if ever. In some cases, a colloid can be considered as ahomogeneous mixture. This is because the distinction between “dissolved”and “particulate” matter can be sometimes a matter of approach, whichaffects whether or not it is homogeneous or heterogeneous.

Classification of Homogeneous Dispersions: Solutions

A solution is a special type of homogeneous mixture. A solution isconsidered homogeneous: (a) because the ratio of solute to solvent isthe same throughout the solution; and (b) because solute will neversettle out of solution, even under powerful centrifugation, which is dueto intermolecular attraction between the solvent and the solute. Anaqueous solution, for example, saltwater, is a homogenous solution inwhich water is the solvent and salt is the solute.

One may also refer to the solvated state, in which a solute ion ormolecule is complexed by solvent molecules. A chemical that is dissolvedin solution is in a solvated state. The solvated state is distinct fromdissolution and solubility. Dissolution is a kinetic process, and isquantified by its rate. Solubility quantifies the concentration of thesolute at which there is dynamic equilibrium between the rate ofdissolution and the rate of precipitation of the solute. Dissolution andsolubility can be dependent on temperature and pressure, and may bedependent on other factors, such as salinity or pH of an aqueous phase.

Solubility Terms

A substance is considered to be “soluble” in a liquid if at least 10grams of the substance can be dissolved in one liter of the liquid whentested at 77° F. and 1 atmosphere pressure for 2 hours and considered tobe “insoluble” if less soluble than this.

As will be appreciated by a person of skill in the art, thehydratability, dispersibility, or solubility of a substance in water canbe dependent on the salinity, pH, or other substances in the water.Accordingly, the salinity, pH, and additive selection of the water canbe modified to facilitate the hydratability, dispersibility, orsolubility of a substance in aqueous solution. To the extent notspecified, the hydratability, dispersibility, or solubility of asubstance in water is determined in deionized water, at neutral pH, andwithout any other additives.

Dielectric constants are not the only measures of polarity butgenerally, dielectric constant of the material provides a rough measureof the material's polarity. As used herein, the term “polar” meanshaving a dielectric constant greater than 15. The term “relativelypolar” means having a dielectric constant greater than about 5 and lessthan about 15 “Non-polar” means having a dielectric constant less than5.

Fluids

A fluid can be a single phase or a dispersion. In general, a fluid is anamorphous substance that is or has a continuous phase of particles thatare smaller than about 1 micrometer that tends to flow and to conform tothe outline of its container.

Examples of fluids are gases and liquids. A gas (in the sense of aphysical state) refers to an amorphous substance that has a hightendency to disperse (at the molecular level) and a relatively highcompressibility. A liquid refers to an amorphous substance that haslittle tendency to disperse (at the molecular level) and relatively highincompressibility. The tendency to disperse is related to IntermolecularForces (also known as van der Waal's Forces). (A continuous mass of aparticulate, e.g., a powder or sand, can tend to flow as a fluiddepending on many factors such as particle size distribution, particleshape distribution, the proportion and nature of any wetting liquid orother surface coating on the particles, and many other variables.Nevertheless, as used herein, a fluid does not refer to a continuousmass of particulate because the sizes of the solid particles of a massof a particulate are too large to be appreciably affected by the rangeof Intermolecular Forces.)

As used herein, a fluid is a substance that behaves as a fluid underStandard Laboratory Conditions, that is, at 77° F. (25° C.) temperatureand 1 atmosphere pressure, and at the higher temperatures and pressuresusually occurring in subterranean formations without applied shear.

Every fluid inherently has at least a continuous phase. A fluid can havemore than one phase. The continuous phase of a well fluid is a liquidunder Standard Laboratory Conditions. For example, a well fluid can inthe form of be a suspension (solid particles dispersed in a liquidphase), an emulsion (liquid particles dispersed in another liquidphase), or a foam (a gas phase dispersed in liquid phase).

As used herein, a water-based fluid means that water or an aqueoussolution is the dominant material of the continuous phase, that is,greater than 50% by weight, of the continuous phase of the substance.

In contrast, “oil-based” means that oil is the dominant material byweight of the continuous phase of the substance. In this context, theoil of an oil-based fluid can be any oil. In general, an oil is anysubstance that is liquid Standard Laboratory Conditions, is hydrophobic,and soluble in organic solvents. Oils have a high carbon and hydrogencontent and are relatively non-polar substances, for example, having adielectric constant of 1.5 to 5. This general definition includesclasses such as petrochemical oils, vegetable oils, and many organicsolvents. All oils can be traced back to organic sources.

Apparent Viscosity of a Fluid

Viscosity is a measure of the resistance of a fluid to flow. In everydayterms, viscosity is “thickness” or “internal friction.” Thus, pure wateris “thin,” having a relatively low viscosity whereas honey is “thick,”having a relatively higher viscosity. Put simply, the less viscous thefluid is, the greater its ease of movement (fluidity). More precisely,viscosity is defined as the ratio of shear stress to shear rate.

A fluid moving along solid boundary will incur a shear stress on thatboundary. The no-slip condition dictates that the speed of the fluid atthe boundary (relative to the boundary) is zero, but at some distancefrom the boundary, the flow speed must equal that of the fluid. Theregion between these two points is named the boundary layer.

A Newtonian fluid (named after Isaac Newton) is a fluid for which stressversus strain rate curve is linear and passes through the origin. Theconstant of proportionality is known as the viscosity. Examples ofNewtonian fluids include water and most gases. Newton's law of viscosityis an approximation that holds for some substances but not others.

Non-Newtonian fluids exhibit a more complicated relationship betweenshear stress and velocity gradient (i.e., shear rate) than simplelinearity. Thus, there exist a number of forms of non-Newtonian fluids.Shear thickening fluids have an apparent viscosity that increases withincreasing the rate of shear. Shear thinning fluids have a viscositythat decreases with increasing rate of shear. Thixotropic fluids becomeless viscous over time at a constant shear rate. Rheopectic fluidsbecome more viscous over time at a constant sear rate. A Bingham plasticis a material that behaves as a solid at low stresses but flows as aviscous fluid at high stresses.

Most well fluids are non-Newtonian fluids. Accordingly, the apparentviscosity of a fluid applies only under a particular set of conditionsincluding shear stress versus shear rate, which must be specified orunderstood from the context. As used herein, a reference to viscosity isactually a reference to an apparent viscosity. Apparent viscosity iscommonly expressed in units of centipoise (“cP”).

Like other physical properties, the viscosity of a Newtonian fluid orthe apparent viscosity of a non-Newtonian fluid may be highly dependenton the physical conditions, primarily temperature and pressure.

Viscosity Measurements

There are numerous ways of measuring and modeling viscous properties,and new developments continue to be made. The methods depend on the typeof fluid for which viscosity is being measured. A typical method forquality assurance or quality control (QA/QC) purposes uses a Couettedevice, such as a Fann Model 35 or 50 viscometer or a Chandler 5550 HPHTviscometer, that measures viscosity as a function of time, temperature,and shear rate. The viscosity-measuring instrument can be calibrated,for example, by using standard viscosity silicone oils or other standardviscosity fluids.

Unless otherwise specified, the apparent viscosity of a fluid (excludingany suspended solid particulate larger than silt) is measured with aFann Model 35 type viscometer using an R1 rotor, B1 bob, and F1 torsionspring at a shear rate of 40 l/s, and at a temperature of 77° F. (25°C.) and a pressure of 1 atmosphere. For reference, the viscosity of purewater is about 1 cP.

A substance is considered to be a fluid if it has an apparent viscosityless than 5,000 cP (independent of any gel characteristic).

Cement Compositions

As used herein, “cement” refers to an inorganic cement (as opposed toorganic cement and adhesives) that when mixed with water will begin toset and harden.

As used herein, a “cement composition” is a material including at leastcement. A cement composition can also include additives. A cementcomposition can include water or be mixed with water.

A cement can be characterized as non-hydraulic or hydraulic.

Non-hydraulic cements (e.g., gypsum plaster, Sorel cements) must be keptdry in order to retain their strength.

Hydraulic cements (e.g., Portland cement) harden because of hydration,chemical reactions that occur independently of the mixture's watercontent; they can harden even underwater or when constantly exposed towet weather. The chemical reaction that results when the dry cementpowder is mixed with water produces hydrates that have extremely lowsolubility in water. The cement composition sets by a hydration process,and it passes through a gel phase to solid phase.

During well completion, it is common to introduce a cement compositioninto an annulus in the wellbore. For example, in a cased hole, thecement composition is placed into and allowed to set in the annulusbetween the wellbore and the casing in order to stabilize and secure thecasing in the wellbore. After setting, the set cement composition shouldhave a low permeability. Consequently, oil or gas can be produced in acontrolled manner by directing the flow of oil or gas through the casingand into the wellhead. Cement compositions can also be used, forexample, in well-plugging operations or gravel-packing operations.

Emulsions

An emulsion is a fluid including a dispersion of immiscible liquidparticles in an external liquid phase. In addition, the proportion ofthe external and internal phases is above the solubility of either inthe other. A chemical can be included to reduce the interfacial tensionbetween the two immiscible liquids to help with stability againstcoalescing of the internal liquid phase, in which case the chemical maybe referred to as a surfactant, an emulsifier, or emulsifying agent.

An emulsion can be an oil-in-water (o/w) type or water-in-oil (w/o)type. A water-in-oil emulsion is sometimes referred to as an invertemulsion. In the context of an emulsion, a “water phase” refers to aphase of water or an aqueous solution and an “oil phase” refers to aphase of any non-polar organic liquid that is immiscible with water,such as petroleum, kerosene, or synthetic oil.

A stable emulsion is an emulsion that will not cream, flocculate, orcoalesce under certain conditions, including time and temperature. Asused herein, the term “cream” means at least some of the droplets of adispersed phase converge towards the surface or bottom of the emulsion(depending on the relative densities of the liquids making up thecontinuous and dispersed phases). The converged droplets maintain adiscrete droplet form. As used herein, the term “flocculate” means atleast some of the droplets of a dispersed phase combine to form smallaggregates in the emulsion. As used herein, the term “coalesce” means atleast some of the droplets of a dispersed phase combine to form largerdrops in the emulsion.

Surfactant or Emulsifier

As used herein, a surfactant or emulsifier refers to a substance thathelps prevent the droplets of the dispersed phase of an emulsion fromflocculating or coalescing in the emulsion. The efficacy of a surfactantis known to be measured using techniques like penetrative displacementand immersion wetting and using parameters like spreading coefficientand partition coefficient.

Surfactants contain both hydrophobic and hydrophilic groups, that is, amolecule that contains both oil soluble as well as water-solublecomponents. These molecules diffuse in water and adsorb at interfacesbetween oil and water. The insoluble hydrophobic group extends out fromthe bulk water phase towards the oil phase while the water-soluble groupremains in the water phase. Alignment of these molecules modifies thesurface properties of the oil-water interface.

A surfactant or emulsifier can be or include a cationic, a zwitterionic,or a nonionic emulsifier. A surfactant package can include one or moredifferent chemical surfactants.

A surfactant package may be included in a fluid that is being deployedfor a clean-out operation. The surfactant package may include one ormore water-soluble surfactants, one or more oil soluble surfactants, andone or more emulsifiers.

General Measurement Terms

Unless otherwise specified or unless the context otherwise clearlyrequires, any ratio or percentage means by weight.

Unless otherwise specified or unless the context otherwise clearlyrequires, the phrase “by weight of the water” means the weight of thewater of the continuous phase of the fluid without the weight of anyviscosity-increasing agent, dissolved salt, suspended particulate, orother materials or additives that may be present in the water.

If there is any difference between U.S. or Imperial units, U.S. unitsare intended.

The barrel is the unit of measure used in the US oil industry, whereinone barrel equals 42 U.S. gallons. Standards bodies such as the AmericanPetroleum Institute (API) have adopted the convention that if oil ismeasured in oil barrels, it will be at 14.696 psi and 60° F., whereas ifit is measured in cubic meters, it will be at 101.325 kPa and 15° C. (orin some cases 20° C.). The pressures are the same but the temperaturesare different—60° F. is 15.56° C., 15° C. is 59° F., and 20° C. is 68°F. However, if all that is needed is to convert a volume in barrels to avolume in cubic meters without compensating for temperature differences,then 1 bbl equals 0.159 m³.

A Method According to the Invention

According to an embodiment, a method is provided including the steps of:

(A) obtaining or providing an apparatus comprising:

(i) a container forming a chamber;

(ii) a first surface exposed to or in the chamber, wherein the firstsurface is of:

-   -   (a) a first electrode, or    -   (b) a first dielectric solid material in contact with the first        electrode;

(iii) a second surface exposed to or in the chamber, wherein the secondsurface is of:

-   -   (a) a second electrode, or    -   (b) a second dielectric solid material in contact with the        second electrode;

wherein the first surface is electrically insulated from the secondsurface;

(B) wetting at least the first surface with a first liquid phase of afirst bulk fluid;

(C) after the step of wetting, introducing a bulk fluid into thechamber, wherein the bulk fluid comprises a second liquid phase, andwherein the second liquid phase is immiscible with the first liquidphase;

(D) applying a shear between the second bulk fluid in the chamber and atleast the first surface; and

(E) making an electrical impedance spectroscopy measurement between thefirst and second electrode.

According to another preferred embodiment of this method, itadditionally includes the steps of: before the step of applying theshear, making a first electrical impedance spectroscopy measurementbetween the first and second electrode; during or after the step ofapplying the shear, making a second electrical impedance spectroscopymeasurement between the first and second electrode; comparing the firstelectrical impedance spectroscopy measurement to the second electricalimpedance spectroscopy measurement; and based on the step of comparing,inferring any changes in the wetting of the first surface. Preferably,the step of inferring comprises assuming an equivalent electricalcircuit model to match experimental impedance changes using non-linearregression techniques.

According to yet another embodiment of the invention, a method isprovided including the steps of: (A) positioning a first electrode and asecond electrode in an annulus between a metallic tubular and theborehole of a wellbore in a well; (B) pumping a fluid through though theannulus and between the first electrode and the second electrode; and(C) at least once during or after the step of pumping, making anelectrical impedance spectroscopy measurement between the first andsecond electrode. It should be understood that the first and secondelectrodes are electrically insulated from the tubular and the flow pathfor electrical current is through the fluid in the annulus.

According to a presently most preferred embodiment, the step of takingan electrical impedance spectroscopy measurement includes: operativelyconnecting an alternating electrical potential source between the firstand second electrodes; while operatively connected to the first andsecond electrodes, varying the electrical potential or the frequency ofthe alternating electrical potential source; and while varying theelectrical potential or the frequency of the alternating electricalpotential source, measuring electrical impedance between the firstelectrode and second electrode to obtain an electrical impedancespectroscopy measurement.

An Apparatus According to the Invention

According to another embodiment of the invention, an apparatus isprovided including:

(A) a container forming a chamber;

(B) a first surface exposed to or in the chamber, wherein the firstsurface is of:

(i) a first electrode, or

(ii) a first dielectric solid material in contact with the firstelectrode;

(C) a second surface exposed to or in the chamber, wherein the secondsurface is of:

(i) a second electrode, or

(ii) a second dielectric solid material in contact with the secondelectrode,

wherein the first surface is electrically insulated from the secondsurface;

(D) a first liquid phase wetted on at least the first surface;

(E) a bulk fluid in the chamber, wherein the bulk fluid comprises asecond liquid phase, and wherein the second liquid phase is immisciblewith the first liquid phase;

(F) a means for controlling the shear rate between the bulk fluid in thechamber and at least the first surface;

(G) an alternating electrical potential source operatively connectedbetween the first and second electrodes;

(H) means for controlling the electrical potential or the frequency ofthe alternating electrical potential source; and

(I) means for measuring changes in electrical impedance between thefirst electrode and second electrode;

whereby electrical impedance spectroscopy measurements can be madebetween the first electrode and the second electrode before, during, orafter controlling the shear rate.

According to a preferred embodiment of this apparatus, the first surfaceis curved.

Applications of the Invention

Various fluids and surfactants are used in wells that may change thewettability or wetting of downhole solid surfaces.

This invention relates to techniques that can be used to test, undersimulated downhole conditions, the surface wetting, film cleaningcapability, or other effect of a fluid on various surfaces. This can beused, for example, to test and quantify the water-wetting efficiency ofa fluid that is to be pumped into a well. It can be used, for example,to test, under simulated conditions, the wetted status of a downholesurface after exposure to a downhole fluid.

According to an embodiment of the invention, a technique of electricalimpedance spectroscopy can be used to measure the percentage area ofcoverage by water or, conversely, area of coverage by oil on a surfaceunder conditions that simulate downhole conditions in a well. Thepercentage of surface wetting with water or oil can be measured usingthis method, non-invasively and without the use of visual inspection, orimaging, or goniometry methods that have been known to be associatedwith error and non-repeatability.

In an embodiment, the invention can be useful in determining thewettability or wetting of surfaces in wells, including the surfaces oftubulars or a subterranean formation. This information can be used inthe design of various well services and well fluids.

In an embodiment, the invention can be used for designing well fluidssuch as drilling fluids, spacer fluids, and cement compositions, or fordesigning the conditions of introducing such well fluids into a well.

In yet another embodiment, the invention can be used as part of a jobfor completing or stimulating a zone in a well.

Applications to Cementing

An example of an application of the invention is to cementing. Hydrauliccement does not bond to oil-wet surfaces. Surface wettability with wateris of primary importance to achieve good cement bonding to a metallicpipe. It is also important to achieve good cement bonding to adjacentrock surfaces of a subterranean formation. The quality of a cement bondto a surface can be expected to be very good if 100% water wetting ofthe surface is achieved.

Calcium, aluminum, and silicon ions of the cement slurry couple byelectrical charges across an interface with ferrous and ferric hydroxideions on the surface of the steel. Iron atoms couple with the unbalancedoxygen atoms in the cement paste. This bonding between the iron atomsand hydroxyl groups in the cement is often described by ahydrogen-bonding coupling with a pair of electrons that are held in theouter fourth orbit of the iron atom.

The cement-steel interface is weaker than the bulk of the cement itself.Increased chances of loss of zonal isolation occur if the completesurface area is not bonded to the cement. Any reduction in thepercentage of water-wet area increases the non-bonded area, therebyreducing the shear bond strength of the cement sheath and its competenceto isolate zones.

Researchers in the area of cement and concrete have previously reportedthat the interface between concrete and steel surfaces is influenced bybleeding and entrapment of water against the surface of the steel andthe less-compact arrangement of the small cement particles that form alayer adjacent to the metal surface. The diameter of the cementparticles is typically in the range of about 10 to about 50 micrometer.The weakest zone at the cement-steel interface during the settingprocess is associated with a porous paste-like zone. This porous pastegradually hardens in the course of the cement slurry setting process andis associated with the formation of ferrous and ferric hydroxides thatare not tightly bonded to the silicate gel in the paste.

A water-wetted metal surface allows for the formation of a stronger andmore completely bonded cement-steel interface. Similarly, a water-wettedrock surface of a subterranean formation allows for the formation of astronger and more completely bonded cement-rock interface. Accordingly,in a cementing operation, it is important to try to change an oil-wettedsurface to a water-wetted surface prior to placing the cementcomposition in the portion of the wellbore to be cemented.

FIGS. 1 a, 1 b, and 1 c are illustrations of a sequence of fluiddisplacement in a wellbore during a cementing operation. A spacer fluid30 is illustrated being pumped into a wellbore of a well penetrating aformation 10 and down through a casing 12 (which has not yet beencemented) and then out the lower end of the casing and up through theannulus 14 between the outside of the casing 12 and the borehole of thewellbore. FIG. 1 a illustrates a drilling mud 20 initially the annulus14 of the wellbore around the casing 12. FIG. 1 b illustrates a spacerfluid 30 being pumped through the casing to displace the drilling mud 20from the annulus 14. FIG. 1 c illustrates a cement composition 40(sometimes referred to as a cement slurry) being pumped through thecasing 12 to displace the spacer fluid 30 and placed in the annulus 14for cementing the casing 12 in the wellbore penetrating the formation10. To seal the annulus 14 with cement requires good cement bondingbetween both the outer wall of the casing 12 and the rock of thesubterranean formation 10 of the borehole.

FIG. 2 is an illustration modeling of fluid intermixing between a priorwell fluid, such as a drilling mud 20, in a wellbore penetrating asubterranean formation 10 and a spacer fluid 30 as the spacer fluiddisplaces the prior drilling mud 20, which is similar to the stageillustrated in FIG. 1 b. In FIG. 2, the spacer fluid 30 is illustratedbeing pumped into the well and down through a casing 12 (which has notyet been cemented) and then out the lower end of the casing and upthrough the annulus 14 between the outside of the casing and theborehole of the wellbore penetrating the subterranean formation 10. Asthe spacer fluid displaces the prior fluid in the wellbore, there is adiffused layer 32 of mixing and channeling between the prior fluid andthe spacer fluid. The diffused layer 32 includes varying mixtures of theprior fluid in the well and spacer fluid. The diffused layer 32 issometimes referred to as contaminated spacer fluid. The spacer fluid 30being pumped behind the diffused layer is sometimes referred to as pureor uncontaminated spacer fluid.

FIG. 3 is a graphical representation of a diffused layer between anoil-based drilling mud and a water-based spacer fluid, wherein at somedegree of mixing and depending on the particular compositions of theoil-based and water-based fluids, the continuous phase of the fluid inthe zone of the well inverts from oil-based to water-based.

A method according to the invention can be used to test theeffectiveness of a water-based spacer fluid for removing an oil-baseddrilling fluid and rendering downhole surfaces water wet prior to cementslurry placement. This method can be used to optimize the dosage ofcostly surfactant packages, annular pump rates, and contact times inspacer fluids at downhole conditions. In addition, the method can beextended to perform quality check on cement to pipe bonding after cementsetting.

Fundamental Electrical Concepts

A conductor is a substance that contains movable electric charges. Inmetallic conductors such as copper or aluminum, the movable chargedparticles are electrons (see electrical conduction). Positive chargesmay also be mobile, such as the cationic electrolyte(s) of a battery, orthe mobile protons of the proton conductor of a fuel cell. In general,the term wire refers to an elongated conductor.

An insulator is a non-conducting substance with few mobile charges andwhich support only insignificant electric currents.

The electrical resistance of an electrical element is the opposition tothe passage of an electric current through that element; the inversequantity is electrical conductance, the ease at which an electriccurrent passes. The SI unit of electrical resistance is the ohm (Ω),while electrical conductance is measured in siemens (S).

A substance of uniform cross section has a resistance proportional toits resistivity and length and inversely proportional to itscross-sectional area. All substances show some resistance, except forsuperconductors, which have a resistance of zero. The resistance (R) ofan object is defined as the ratio of voltage across it to currentthrough it, while the conductance (G) is the inverse.

Permittivity is a measure of the ability of a material to be polarizedby an electric field. The dielectric constant of a material is the ratioof its permittivity to the permittivity of vacuum. The dielectricconstant is therefore also known as the relative permittivity of thematerial. More particularly, in electromagnetism, absolute permittivityis the measure of the resistance that is encountered when forming anelectric field in a medium. In other words, permittivity is a measure ofhow an electric field affects, and is affected by, a dielectric medium.The permittivity of a medium describes how much electric field (morecorrectly, flux) is “generated” per unit charge in that medium. Lesselectric flux exists in a medium with a high permittivity (per unitcharge) because of polarization effects. Permittivity is directlyrelated to electric susceptibility, which is a measure of how easily adielectric polarizes in response to an electric field. Thus,permittivity relates to a material's ability to transmit (or “permit”)an electric field.) In SI units, permittivity ∈ is measured in faradsper meter (F/m); electric susceptibility χ is dimensionless.

The continuous phase of a fluid characterizes the relative permittivityof the fluid as a whole.

Electrical Double Layer and Capacitance

Without being limited by any theory, it is postulated that theproduction of an electrical double layer (“EDL”) occurs when a chargedsurface comes into contact with a polar or ionized liquid.

An electrical double layer is a structure that is formed on the surfaceof a charged object when it is placed in contact with a liquid. Theelectrical double layer is a structure that describes the variation ofelectric potential near a charged surface in contact with a liquid.

The surface charge on the object creates an electrostatic field thatthen affects the ions in the bulk of the liquid. This electrostaticfield, in combination with the thermal motion of the ions, creates acounter charge, and thus screens the electric surface charge. The netelectric charge in this screening, diffuse layer is equal in magnitudeto the net surface charge, but has the opposite polarity. As a result,the complete structure is electrically neutral. Some of the counter-ionsmay specifically adsorb near the surface and build an inner sub-layer,or so-called Stern layer. The Stern Layer is typically of the angstromrange because of the extreme proximity of the opposite charged atomsco-existing in line. The outer part of the screening layer is usuallycalled the diffuse layer. An electrical double layer on a positivelycharged surface is illustrated in FIG. 4.

The diffuse layer, or at least part of it, can move under the influenceof tangential stress. A slipping plane separates mobile fluid from fluidthat remains attached to the surface. FIG. 5 is an illustration ofelectric potential distribution of an electrical double layer based onthe dielectric dipole moment (i.e., Debye length) of the molecules ofthe liquid medium, including showing the region of the slipping plane.

An electrical double layer is often characterized by a parameter calledthe electrical double layer capacitance (“EDLC”). Capacitance is afunction of the dielectric constant of the liquid medium present inbetween the charged particles in the liquid medium. Thus, the chargedistribution on a charged surface is different for polar fluids (such aswater-based well fluids, including aqueous spacer fluids and cementingslurries) and non-polar fluids (such as diesel, ester, or the other baseoils used in oil-based drilling fluids). For the purpose ofillustration, if the dielectric constant of non-polar fluids is assumedto be 20 times less than that of water. Therefore, a 20-fold increase inthe capacitance can be expected in a linear variation from 100% oil wetto 100% water wet if the double layers were modeled as ideal capacitorsin parallel, keeping the electrolyte constant. This difference in chargedistribution patterns affects the value of double layer capacitance.Increasing percentage of surface coverage with water will thereby leadto an increase in double layer capacitance. Typically, on a conductingbare metal immersed in an electrolyte, approximately, 10 to 50microfarad of capacitance appears on every square centimeter on theelectrode. A conducting bare metal immersed in an oil-based fluid wouldhave a much lower electrical double layer capacitance.

Electrical Impedance Spectroscopy to Test Wetting in a Complex System

Well fluids and downhole surface conditions are complex systems. Indealing with particle-laden well fluids on irregular and rough surfaces,the concept of ideal capacitor may turn out to be insufficient.Temperature, ionic concentration, types of ions, oxide layers,adsorptive species, and surface roughness influence electrical doublelayer capacitance. According to the invention, these are modeled ascapacitors that are leaky and that have non-uniform currentdistribution. In addition, when a surface is polarized, it can causecurrent to flow through electrical interactions that are induced tooccur at or near the surface. These effects can be modeled usingparameters known as polarization resistance and charge transferresistance. Electrical interactions accompanied by mass transfer aremodeled using a parameter known as Warburg Impedance.

According to the invention, a combination of resistors and capacitors isused to model the impedance offered by a system. The impedance offeredby the system is physically measured and subsequent mathematicalmodeling is carried out to calculate the values of the resistances andcapacitances of the individual electrical elements. These values will bean indication of the completeness of water wetting on the surface.

An electrical circuit is completed in order to measure the impedance ofthe system. This can be done by building an electrical system with anoil-field well fluid.

In general, an AC circuit is used to measure impedance at a perturbationvoltage and various frequencies.

Electrical properties that influence charge conductance or accumulationassociated with the surfaces can be additionally modeled with thistechnique to study or simulate changes in the wetting on a surface in awell.

According to an embodiment for simulating downhole conditions on ametallic surface, an electrical system 100 is schematically represented,in FIG. 6 a and FIG. 6 b. As shown in FIG. 6 a, the electrical system100 includes: an electrically insulating electrode holder or container110, a first electrode 120; a second electrode 130, an optionalreference electrode 140, a motor (not shown) for providing rotationalspeed Ω to a structure 160 for shearing a fluid in the container 110,wires 152 and 154 operatively connected between the first electrode 120and the second electrode 130, respectively, to an EIS measuring device(not shown in this figure).

This system 100 is adapted for simulating and measuring the formation orremoval of any wetting or coating or film 170 on the surfaces theelectrodes 120 or 130 in the presence of a test fluid 180. The changescan be measured under shearing conditions applied to the test fluid 180in the system 100. The composition of the test fluid 180 can be keptconstant during a testing procedure or it can be changed continuously orintermittently by dosing another test fluid that displaces the originalfluid under controlled hydrodynamic conditions. In general, the systemand applied voltage is adapted such that the electrical circuit isdirected across the electrodes 120 and 130 through the test fluid 180.FIG. 6 b is a top view of FIG. 6 a.

One or both the electrodes 120 and 130 can be used to simulate adownhole metallic material, such as a steal tubular, the test conditionsof shear, and optionally temperature and pressure can be adapted tosimulate downhole conditions adjacent a downhole metallic material, andthe test fluid can be used to simulate a well fluid in a wellbore. Ingeneral, the system 100 can be used, as described herein, to measure anychanges in any surface wetting or film 170 on the test electrodes undersuch simulated test conditions and with such test fluids.

The system 100 can be used to determine the removal of a film or coatingon an metallic electrode surface that is needed to be removed under theeffect of shear, pressure, temperature, and time conditions as may beused in the wellbore. Here, the coating can be deliberately created byapplying a coating manually or can be automatically created during theprocess of shearing the fluid which is responsible for applying thecoating in the setup. In this case, the contents and ingredients of thecoating will be present in the first fluid. The second fluid will beused to remove the coating.

In one type of test procedure, for example, the second bulk fluid ispoured into the container of the apparatus in the event where the filmof a first liquid phase is first manually created.

In another type of procedure, for example, the coating or film iscreated by a first bulk fluid on the surfaces under the effect ofpressure, temperature, and shear, and time. The second bulk fluiddisplaces the first bulk fluid, preferably under simulated wellconditions of pressure, temperature, shear, and time. Any removing orcleaning the prior film on the surface under the controlled hydrodynamicconditions can be objectively measured with electrical impedancespectroscopy according to the invention.

According to an embodiment for simulating downhole conditions on a rocksurface, an electrical system 200 is schematically represented, in FIG.7 a and FIG. 7 b. FIG. 7 a is a vertical cross-sectional view of anelectrical apparatus for measuring the change in surface wetting on adielectric solid surface, which can be selected, for example, tosimulate a rock surface of a subterranean formation. The electricalcircuit for measuring electrical impedance between the electrodes of theapparatus is not shown in detail.

As shown in FIG. 7 a, the electrical system 200 includes: an insulatingelectrode holder or container 210, a first electrode 220, which iscentered in concentrically located formation material 222; secondelectrodes 230 a and 230 b, which can be the same as each other; anoptional reference electrode 240, a motor (not shown) for providingrotational speed Ω to a structure 260 for shearing a fluid in thecontainer 210, wires 252 and 254 operatively connected between the firstelectrode 220 and the second electrodes 230 a and 230 b to an EISmeasuring device (not shown in this figure). It should be understoodthat two of the second electrodes 230 a and 230 b are not required, butrather, one of the second electrodes would suffice, if desired.

This system 200 is adapted for simulating and measuring the formation orremoval of any wetting or coating or film 270 on the surfaces of theformation material 222 in the presence of a test fluid 280. The changescan be measured under shearing conditions applied to the test fluid 280in the system 200. The composition of the test fluid 280 can be keptconstant during a testing procedure or it can be changed continuously orintermittently by dosing another test fluid that displaces the originalfluid under controlled hydrodynamic conditions. In general, the systemand applied voltage is adapted such that the electrical circuit isdirected across the electrodes 220 and 230 a and 230 b through the testfluid 280. FIG. 7 b is a top view of the apparatus in FIG. 7 a,illustrating the insulated separation of the dielectric surfaces in thecontainer wall of the apparatus.

It should be understood, of course, that the dielectric constant of theinsulating material of the container 210 of the system 200 should belower than that of any liquid phases being tested for wetting on thetesting surface. Similarly, it should be understood, of course, that thedielectric constant of the insulating material of the container shouldbe lower than that of the material of the testing surface. A firstelectrode is placed in electrical contact with the dielectric solid tobe tested. This type of apparatus can measure the change in surfacewetting on a tested dielectric surface from a first liquid phase to asecond liquid phase as a second bulk fluid including the second liquidphase is sheared in the container of the apparatus at a controlled ratefor a controlled contact time. The dielectric solid surfaces can beselected to simulate the rock of a subterranean formation in a well. Thefirst liquid phase can simulate a prior oleaginous film formed on thesurface of the rock. The second bulk fluid can and conditions of shearand time can simulate the displacement of the oleaginous film by aspacer fluid.

FIG. 8 is a vertical cross-sectional view of an alternative electricalapparatus 300 for measuring the change in surface wetting on adielectric solid surface, which can be selected, for example, tosimulate a rock surface of a subterranean formation. As illustrated inFIG. 8, in this embodiment the rock surface is axially separated fromanother electrode exposed to a bulk fluid in the chamber of thecontainer.

As shown in FIG. 8, the electrical system 300 includes: an insulatingholder or container 310, a first electrode 320, which is concentricallylocated in the bottom of a sample of formation material 322; a secondelectrode 330 toward the top of the apparatus 300, rotational speed Ω(provided by a motor not shown); a plurality of wires including 352 and354 from the first electrode 320 and second electrode 330 to an EISmeasuring device (not shown); a shearing structure 360 extendingdownward into the container 310; bushings 362 for the stirring rod, andat least one, preferably a plurality, of fluid-tight O-rings 390 betweenthe second electrode 330 and the container.

This system 300 is adapted for simulating and measuring the formation orremoval of any wetting or coating or film 370 on the surfaces of theformation material 322 in the presence of a test fluid 380. The changescan be measured under shearing conditions applied to the test fluid 380in the system 300. The composition of the test fluid 380 can be keptconstant during a testing procedure or it can be changed continuously orintermittently by dosing another test fluid that displaces the originalfluid under controlled hydrodynamic conditions. In general, the systemand applied voltage is adapted such that the electrical circuit isdirected across the electrodes 320 and 330 through the test fluid 380.

It should be understood, of course, that the dielectric constant of theinsulating material of the container 310 of the electrical system 300should be higher than that of any liquid phases being tested for wettingon the testing surface. This type of apparatus can measure the change insurface wetting on a tested dielectric surface from a first liquid phaseto a second liquid phase as a second bulk fluid including the secondliquid phase is sheared in the container of the apparatus at acontrolled rate for a controlled contact time. The dielectric solidsurfaces can be selected to simulate the rock of a subterraneanformation in a well. The first liquid phase can simulate a prioroleaginous film formed on the surface of the rock. The second bulk fluidcan and conditions of shear and time can simulate the displacement ofthe oleaginous film by a spacer fluid.

FIGS. 9 a and 9 b are vertical cross-sectional views illustrating anembodiment depicting direct electrical measurements in a well, which canbe used, for example, during the real-time pumping operations todetermine any change in wetting of a downhole tubular surface during awell operation such as cementing. FIG. 9 a is a vertical cross-sectionalview of a portion of a metallic tubular, such as a casing, positioned ina wellbore. FIG. 9 b is a detail view of an electrical probe deviceassociated with a portion of the casing in the wellbore. According tothis embodiment of the invention, a measurement of the surface wettingof a metallic sample material that is similar to a casing material inthe well is obtainable directly situated in the downhole environment.

As shown in FIG. 9 a, the system 400 of this embodiment includes: a wellpenetrating a formation 10, a metallic tubular, such as a casing 12,positioned in the wellbore of the well, which forms an annulus 14between the outside the casing and the wellbore. Similar to theillustration of the situation in FIG. 2, a drilling mud 20 is shownbeing displaced by a spacer fluid 30, which during displacement forms adiffused layer 32 and a contaminated spacer fluid layer 34. In thisembodiment, there is a zone of cementing interest, that is, a zone forwhich a good placement and bonding of cement to the metallic surface ofthe casing 12 is desired. One or more electrical probe devices, such asprobe devices 401 a and 401 b, are operatively deployed adjacent aportion of the casing in or near the zone of cementing interest, forexample, at position Zone 1 or position Zone 2. As shown in FIG. 9 a,electrically insulated wires 452 and 454 extend uphole to the surfacefrom each of the probe devices 401 a and 401 b.

FIG. 9 b is an illustration of the electrical probe device 401 a.Electrical probe device 401 b can be substantially similar to electricalprobe device 401 a. It can be for measurement redundancy or makingmeasurements along more than one position in the zone of cementinginterest.

The electrical probe device 401 a should be electrically insulated fromthe metallic casing 12, however, so as to avoid an undesired circuitpath. Accordingly, in this embodiment, the probe 401 a device includesan electrically insulating sleeve 410 to insulate a first electrode 420and a second electrode 430 from the metallic casing 12 and to supportthe first and second electrodes apart from each other in the annulus 14.The first electrode 420 and the second electrode 430 are operativelyconnected to an EIS measuring device at the surface through insulatedelectrical wires 452 and 454. It should be understood, of course, thatthe dielectric constant of the insulating sleeve 410 should be lowerthan that of any liquid phases being tested for wetting on either of thefirst electrode 420 or second electrode 430 in the well. Measuring thewetting on the first or second electrodes with EIS can be used todetermine the wetting on the adjacent casing.

Electrical Wire and Electrodes

Electrical wire refers to an elongated metallic conductor that iscovered with an electrically insulating material. Electrical wire isused to carry electricity.

An electrode is a metallic electrical conductor used to make contactwith a non-metallic part of a circuit (e.g. a semiconductor, anelectrolyte, or a vacuum).

A first electrode is used in conjunction with a second electrode. Inaddition, sometimes a reference electrode is used in a three-electrodesystem.

The first electrode can be an electrode in an electrical system on whichthe change of interest is occurring. In a two-electrode system, either aknown current or potential is applied between the first and secondelectrodes and the other variable may be measured.

When a three-electrode cell is used, the first or second electrode,along with the reference electrode, provides a circuit over whichcurrent is either applied or measured. This configuration allows thepotential of the first or second electrode to be measured against aknown reference electrode without compromising the stability of thereference electrode by passing current over it.

In measuring for the purposes of determining the changes in anelectrical double layer or film on a surface, the electrical system isoperated at a current or potential below that which would cause a redoxreaction in the chemical species present in the system.

Selecting First Electrode for Downhole Surface to be Simulated

The first electrode is preferably made of the same metallic material asa downhole material, such as a metal tubular, for which any change ofwater wettability or wetting is to be simulated and determined. Thesurface of the first electrode can be modified by roughening, polishing,mill varnishing, etc., or it can be a corroded piece of the material,depending on the condition of the downhole tubular to be simulated. Thefirst electrode can be made initially water wetted or oil wetted asdesired, to simulate the condition of a downhole surface.

Selecting Second Electrode

The second electrode can be the same as the first electrode, in whichcase standardization in the experimental method demands that the firstelectrode and second electrode be machined out of the same piece ofstock to ensure the same averaged characteristics on both theelectrodes. Alternatively, the second electrode can be made of anon-corrosive conductive material, such as platinum or graphite, as astandard material. For the ability to compare between labs andcompanies, it would be preferable to use standard materials as thecounter electrode and have an option to use specific well materials ifdesired. Using standard platinum or graphite electrodes as the counterelectrode would eliminate the need to change both the electrodes fortesting different materials.

Preferably, the surface area, aspect ratio, and surface to volume ratioof each of the first and second electrodes is as close as practical toeach other for symmetry in the electrical test system.

Optional Reference Electrode

Preferably, a reference electrode is mounted in the electrical system inclose proximity to the first electrode. A reference electrode is anelectrode that has a stable and well-known electrode potential. Thepurpose of the reference electrode is to make sure that the potential ofthe first electrode remains constant with respect to the ground. Thissystem is analogous to a 3-point potentiostat system.

The reference electrode can be, for example, a standard calomelelectrode or an Ag electrode in AgCl solution.

Selecting Test Bulk Fluid

The test bulk fluid can be selected to simulate a well fluid or downholefluid.

For example, when a water-based spacer fluid is used to displace anoil-based drilling fluid (also known as an oil-based drilling mud) inthe annulus prior to pumping cement, a concentration gradient can beclearly noticed at the interface of the spacer fluid and drilling fluid.This concentration gradient is due to mass and momentum transport owingto the differences in densities and rheologies of the bordering fluids,and is better known in the industry by various names, such asintermixing, channeling, and fingering.

A surfactant package of one or more surfactant chemicals is usuallyincluded in the water-based spacer fluid to make a stable,water-external emulsion when the water-based fluid mixes with anoil-based fluid, such as an oil-based drilling mud. The surfactantpackage can include, for example, a combination of: (a) oil-solublesurfactant; (b) water-soluble surfactant; and (c) emulsifier. Thesurfactants are believed to make the emulsion water external and oilinternal.

People skilled in the art of designing cement jobs would appreciate thatachieving water wet surfaces downhole is a tradeoff between thesurfactant concentrations and contact volumes and concentrations. Aninitial spacer/mud volume ratio needs to be fixed and the surfactantpack optimization is carried out at that fixed ratio. If a surfactantpack optimization is planned at 25/75 spacer/mud concentration,obviously more surfactant will be needed to make a stable water externalemulsion. If it is planned at 75/25 spacer/mud concentration, not enoughfully water-wetting spacer is left behind to carry out the cleaningoperation.

Previous methods discuss optimizing the surfactant package by testing toachieve full bulk conductivity in the emulsion. When the bulkconductivity of the emulsion remained constant at all shear rates andequal to that of the pure water-based spacer fluid, it was concludedthat the emulsion was a stable emulsion and would not invert back tobecome unstable. This measures the solution bulk resistivity at only asingle frequency, typically 50 Hz or 60 Hz, whichever frequency islocally available. This only gives information on the conductivity ofthe solution alone, but does not give any information about anyinterfacial phenomena.

Blending of two phases in the bulk of a fluid system under the effect ofshear does not complete cleaning on surfaces. For correct design ofoperational parameters and fluid systems to meet the design intent ofachieving complete surface wetting, it is critical to simulate the bulkshear rates and wall shear rates in an experimental setup at thelaboratory scale or via pilot testing to be nominally equivalent to theshear rates expected to be experienced downhole.

Interfacial tension of oil-water phases is reduced by fit-for-purposesurface-active agents under shear causes emulsion to be inverted,thereby changing the continuous external phase from oil to water orvice-versa. US Statutory Invention Registration H1932, dated Jan. 2,2001, entitled “Wettability and Fluid Displacement in a Well.” which isincorporated herein by reference in its entirety, discusses methods andapparatuses used for measuring this phenomena by measuring a propertyrelated to the electrical conductivity of the emulsion during theinversion process. A drastic change in electrical conductivity isobserved when the inversion occurs. The apparatus consists of a blenderjar with a blade at the bottom and electrodes that are built into thejar to measure electrical conductivity. However, the deficiencies ofthat disclosure include: (1) shear rate profiles and distribution arenot similar to the wellbore; (2) shear rates are not quantifiable; (3)resolution of the apparatus is not fine enough to capture differences inconductivity with varying percentage of water wetting on the electrodes;(4) electrodes are contact pins that have very low surface area comparedto the mixing geometry; (5) the property being measured is a bulkproperty and not a surface property; and (6) formation surfaces are notadequately simulated because only small metal pins act as electrodes.

For example, a problem with the US H1932 is that although there are twoelectrodes in the test cup that are insulated from the cup, the cup ismade of metal. So for this system, if there is a water wetting of aportion of the seal (or the entire seal behind the electrode), the pathof least electrical resistance is not across the fluids to the otherelectrode, but only about 1/16 inch from the electrode to the metalmixer container, around the metal container to the second electrode, andthen about 1/16 inch to the second electrode. In a system according tothe present invention, the electrodes are larger and fully insulatedfrom the cup so there can be no path between the cup and the electrodes.The conductance (resistance) of the fluid between the electrodes, withadditional impedance measurements, are used to measure how much of theelectrode is or has become water wet.

It is occasionally noticed, however, that even though full bulkconductivity is achieved, patches of non-aqueous film are still presenton the walls of the mixer that is used to carry out the bulkconductivity experiments. US Patent Publication No. 2011/0005310,published Jan. 13, 2011, entitled “Methods for Contacting a Surface witha Fluid Containing a Marker to Determine the Wettability of theSurface,” which is incorporated herein by reference in its entirety,discloses a visual inspection method based on a dye to qualitativelystudy surface wetting. They demonstrated the transition from partiallywater-wet condition to fully water-wet condition on the surface byincreasing the concentration of surfactant package. Unfortunately, thepercentages of surface wetting are not easy to measure. It has also beenobserved that though bulk water wetting is achieved for a particularcomposition in this set up, there are particles of non-aqueous film onthe surface of the jar. Moreover, it is well known from literature thatsurface wettability depends on the roughness, electrical charge, andreactivity of the surface in question. This patent shows the occurrenceof non-aqueous film and describes a visual imaging technique to quantifythe same. The challenges associated with visual imaging include: (1)poor repeatability; (2) operator error associated with imaging andphotosensitivity; (3) properties of dyes/markers that may interfere withthe chemical reactivity of the system; (4) difficulty in performingunder High Pressure and High Temperature (“HPHT”) conditions; (5)difficulty with imaging while in-situ owing to the presence of particleladen or dirty fluids; (6) difficulty with creating images on surfacesthat are curved; (and (7) shear rate values not objective andquantifiable.

According to the present invention, methods and apparatuses are providedthat overcomes the challenges associated existing techniques thatinclude: (1) quantifiable shear; (2) HPHT conditions; (3) workabilitywith particle lade or dirty fluids; (4) ability to study the effect ofcontact time; (5) additional capability to study how much wall shearstress is needed to overcome the surface tension/cohesion/adhesioneffects associated with non-polar surface films. These findings can thenbe applied to job design for determining fluid properties andoperational parameters like pump rates and contact times.

To replicate the downhole conditions and to carry out meaningfultesting, a concentration ratio needs to be first fixed and hence, theelectrolyte is chosen to be a mixture of an oil-based well fluid and awater-based well fluid in the desired concentration. The water-basedwell fluid can have a known concentration of surfactant package alreadypremixed.

A coating (layer of oil based mud, filter cake, silicate coating, etc.)whose dielectric properties are different from that of the fluid used(inverter fluid or spacer) for cleaning the coating may be pre-appliedand the electrolyte can be the pure, uncontaminated inverter or spacerfluid to simulate the flow behavior in the annulus below the diffuselayer. FIGS. 6 a-6 b, 7 a-7 b, 8, and 9 a-9 b show schematicrepresentation of various electrical systems where a film can be appliedto a surface and subjected to shear by another bulk fluid for thepurposes of measuring changes in wetting on the surface.

Alternately, the fluid that is responsible for creating the coating(drilling mud) may be replaced completely with a wash, spacer orinverter fluid while going through an optional process of generatinghomogenous admixtures with incremental variation on the volumetricratios between both the fluids. The electrical properties associatedwith this setup can be monitored to understand the displacement and thedynamics of coating removal. FIGS. 6 a-6 b, 7 a-7 b, 8, and 9 a-9 b showthe schematic representation of electrical systems where the non-aqueousmaterial will be displaced by a water-wettingwash/spacer/inverter-fluid, while facilitating the application of shearand impedance measurement simultaneously.

Impedance Spectroscopy and Modeling

An alternating current electrical potential difference is applied inbetween the first and second electrodes and the alternating currentflowing in between them is measured. The potential difference needs tobe at least sufficient to form a measurable electrical circuit through afluid between the first and second electrode.

The ratio of the voltage to alternating current flowing across the firstand second electrodes is termed as impedance. Unlike resistance, whichis a simple linear quotient between voltage and current, impedance is acomplex number. When this voltage is alternating in nature, and isapplied at various frequencies in the range of 1 microHertz to 1gigaHertz, and the current responses to these frequencies are measuredat the respective frequencies, impedances can be calculated in thefrequency domain to give crucial information about bulk, interfacial,and electro-kinetic processes in the system.

Impedance is measured using a pseudo-linear or small signal response. Ina pseudo-linear system, the current response to a sinusoidal potentialwill be a similar sinusoidal signal at the same frequency, but with alag in phase as shown in FIG. 10.

The excitation potential is of the form of Equation 2:

V=V ₀ sin(ωt)  Eq. 2

where V₀ is typically in the range of about 1 mV-100 mV to make it apseudo-linear system.

Then, the current response signal is of the form of Equation 3:

I=I ₀ sin(ωt+φ)  Eq. 3

The impedance of the signal can be calculated analogous to Ohm's law asEquation 4:

Z=V/I=V ₀ sin(ωt)/I ₀ sin(ωt+φ)=Zo sin(ωt)/sin(ωt+φ)  Eq. 4

This is often transformed into the frequency domain to represent in acomplex number form and is represented in Equation 5.

Z(ω)=Z ₀exp(jφ)=Z ₀(cos φ+j sin φ)  Eq. 5

The complex number Z is composed of a real part and an imaginary part. Arepresentation of the imaginary part plotted on the y-axis against thereal part of the x-axis, is called the Nyquist plot.

Bode plots represent variation of |Z| and φ as a function of ω.

These plots can be analyzed in terms of an equivalent circuit model andmodel parameters are fitted using Non Linear Regression techniques.Initial guess of the closest applicable model and the values of thecapacitance and resistance contributed by individual elements in thesystem (electrolyte, electrode, and auxiliary connections) can beinferred from the shape and inflexions on the Nyquist and Bode plots.

According to the invention, a technique of impedance spectroscopy isapplied to model the wettability or wetting of a metal surface, may bedone for example as illustrated in the circuit models shown in FIG. 11and FIG. 12, where the system includes solution bulk resistance,non-polar layer capacitance, polarization resistance, charge transferresistance, and double layer capacitance between the surface of thefirst electrode and the second electrode. Depending on the physicalscenario, one of many of these circuit elements may be missing in theequivalent circuit model that best fits the impedance data.

For example, the best fitting equivalent circuit can be a Failed PaintModel (FP) circuit model as shown in FIG. 11 or a Constant Phase Elementwith Diffusion (“CPED”) circuit model as shown in FIG. 12.

From theoretical point of view, as the non-aqueous film gets cleanedfrom the surface of the electrodes, it is expected that the value ofdouble layer goes up and the other components like charge transferresistance, or polarization resistance go down. For example, if thebest-fit equivalent circuit is Failed Paint Model (“FP”) model, then theNyquist and Bode plots are shown in FIG. 13 and FIG. 14, respectively,depicting the cases of before and after changing an oil-wetted surfaceto a water-wetted surface.

An example of a Nyquist plot according to a CPED model before and afterwetting is shown in FIG. 15. Experimentally, a similar variation ofNyquist plot is observed for varying fractional surface covered withnon-aqueous film (“NAF”), as shown in FIG. 16. An example of a Bodemagnitude plot according to a CPED model before and after water-wettingis shown in FIG. 17. Experimentally, a similar variation of Bodemagnitude plot is observed for varying fractional surface covered withnon-aqueous film (“NAF”), as shown in FIG. 18.

It can be seen from FIG. 16 and FIG. 18 that, as the percent coverage ofnon-aqueous film increases, the magnitude of impedance increasedproportionately. In addition, the CPED model is found to fit the datathrough EIS modeling and the double layer capacitance, as obtained fromthe analysis, decreased linearly as the percent coverage of non-aqueousfilm coverage is increased.

As the fraction of electrode surface that is coated withnon-water-wetting film increases, we expect the capacitance readingshown by an LCR meter to reduce linearly because the double-layercapacitance is a surface phenomenon, which occurs at charged surfaces incontact with conducting interfaces.

The following two combinations of non-aqueous-film and electrolyte werestudied in the above-described manner: (a) grease as film and salt-watersolution as electrolyte, as shown in FIG. 19; (b) oil-based mud as filmand salt-water solution as electrolyte, as shown in FIG. 20. Themeasured capacitance is plotted as a function of percent coverage ofnon-aqueous film on the electrode. All the above three combinations arefound to follow a linear trend, all having a least squares fit (R²)better than 0.99, as shown in FIGS. 19-20.

This shows that the capacitance can be used as an indirect measure ofthe surface wettability or wetting.

To account for non-ideal effects, the combination of charge transferresistance and double layer capacitance may be modeled using a constantphase element (α) following the Equation 6:

$\begin{matrix}{{Z_{1}(\omega)} = \frac{R_{ct}}{1 + \left( {{j\omega}\; R_{ct}C_{dl}} \right)^{\alpha}}} & {{Eq}.\mspace{14mu} 6}\end{matrix}$

With increase in surface water wetting, when such a model is used, it isexpected that the values of double layer capacitance and capacitanceused to model the non-polar layer will sharply increase due toincreasing efficiency of polarization and appearance of opposite chargesnear the electrode. The value of polarization resistance and chargetransfer resistance is expected to decrease sharply.

The value of the solution bulk resistivity is expected to remainconstant from the point any mixture of a water-based fluid and anoil-based fluid forms an emulsion that becomes completely water externalwhile other parameters change during the course of the surface wettingoperation. If the electrolyte is changed by forming admixtures withincremental concentration levels during the process of displacing onefluid with the other, all parameters are expected to change—therefore a“control experiment” needs to be carried out to determine the electricalparameters of a system with no coating and pure fluid in place. Thevalues derived during the course of the experiments will then need to becompared with the control experiment in order to determine whether afully wet surface with a well fluid has been achieved. It should beunderstood that the well fluid can be, for example, a pure a wash fluid,an inverter fluid, a spacer fluid, or a lead cement composition.

The magnitude of the frequency directly relates to the time scale ofspecies and charge transport. As an example, the bulk transport of massand charge correspond to time scales of 10⁻⁶ sec and are thereforeinferred at high frequencies. It can be seen that corrosion, which is a“long term” process, can be predicted at low frequencies that correspondto time scales of the order of 1000 seconds.

For example, when the technique is used with cement slurry electrolyte,the high frequency response (kHz-MHz) may be used to infer conclusionsabout the bulk parameters like bulk conductivity, diffusivity, andpermeability of the cement paste. The intermediate frequency (Hz-kHz)data may be analyzed to provide information about the nature of the nearinterface zone and the formation of any porous diffuse layer(oxide/carbonate film, etc.) on the first electrode. The low frequencyresponse (mHz-Hz) provides information on the passive behavior of thesteel and corrosion related electro-kinetic reactions.

FIG. 21 is a graph of inferred double-layer capacitance vs. percentcoverage of several different combinations of non-aqueous films inwater-based bulk fluids from electrical measurements in an electricalcell using an identical first electrode and second electrode.

In a similar kind of system to that shown in FIG. 6 a, a cylindricalnylon block is machined into a tubular shape and two electrodes areembedded on the inner side of it. A spacer fluid is poured into thenylon block, and impedance data is collected. Spacer fluid is removedand the nylon block is cleaned. A layer of non-aqueous film is placed onthe electrodes, and before filling the nylon block with fresh spacerfluid and impedance data is collected. Impedance data collection isrepeated, after regular intervals of shear (applied using a cylindricalrod inserted into the fluid, and rotated by using a motor).

FIG. 22 shows Bode magnitude plots at different durations of shear forthe measuring of the effect of contact time with 0.05 gal/bbl surfactantconcentration in an aqueous bulk spacer fluid, where the surfactant isan equiproportional mixture of surfactants including alcohol ethersulfate, a low hydrolipic balance non-ionic nonylphenol, and a highhydrolipic balance non-ionic nonylphenol, after following the steps of:(1) placing a spacer fluid in the test cell and taking EIS measurement;(2) starting from a state where the electrodes are coated withnon-aqueous film and the test cell is filled with the spacer fluid at noshear and taking EIS measurements; and (3) shear is applied by rotatinga cylindrical bob at 900 RPM in a configuration similar to as shown inFIGS. 6 a and 6 b and EIS data is recorded at intermittent times of 1minute increments from 1 minute to 7 minutes.

It is observed in FIG. 22 that as the shearing process is continued, theimpedance data approached that of a system where there is no non-aqueousfilm. This is additional evidence that shows this technique can be usedto measure the surface wettability or wetting. It is anticipated to takethese experiments to the next level by simulating shear at ambientconditions and at high-pressure high-temperature conditions to simulatedownhole conditions in a well.

FIG. 23 shows Bode magnitude plots for the experiment in FIG. 22repeated with 0.1 gal/bbl surfactant concentration.

FIG. 24 shows Bode magnitude plots for Experiment in FIG. 22 repeatedwith 0.2 gal/bbl surfactant concentration, at intermittent times of1-minute increments from 1 minute to 3 minutes.

FIG. 25 shows experimental Bode magnitude plots showing the effect ofshear rates after following the steps of: (1) placing pure spacer fluidin the test cell and taking EIS measurement; (2) starting from a statewhere the electrodes are coated with non-aqueous film and the test cellis filled with the spacer fluid at no shear and taking EIS measurements;and (3) shear is applied by rotating a cylindrical bob for 60 seconds atdifferent RPMs of 900 RPM, 1200 RPM, and 1250 RPM in a configurationsimilar to the apparatus illustrated in FIGS. 6 a and 6 b and EIS datais recorded at 1 minute.

Hence, it is believed that impedance spectroscopy can be applied as atechnique to gain information about interface and electro-kineticeffects. It is believed this technique can be extended to study thedielectric response of surfaces and porous and conducting formations.

Additional Embodiments of Methods and Apparatuses

According to an embodiment of the invention, a method is provided,wherein the method includes the steps of:

(A) selecting a test material for a surface to be wetted;

(B) selecting a test bulk fluid;

(C) testing a system of the test material and the test bulk fluid withimpedance spectroscopy to determine the surface wettability or wettingof the test material with the test bulk fluid under conditions thatsimulate downhole well conditions.

The testing can be conducted at any convenient location, including in aremote laboratory or in the field at or near the well site.

More particularly according to a preferred embodiment of the invention,a method is provided including the steps of: provided including thesteps of:

(A) obtaining or providing an apparatus comprising:

(i) a container forming a chamber;

(ii) a first surface exposed to or in the chamber, wherein the firstsurface is of:

-   -   (a) a first electrode, or    -   (b) a first dielectric solid material in contact with the first        electrode;

(iii) a second surface exposed to or in the chamber, wherein the secondsurface is of:

-   -   (a) a second electrode, or    -   (b) a second dielectric solid material in contact with the        second electrode;

wherein the first surface is electrically insulated from the secondsurface;

(B) wetting at least the first surface with a first liquid phase of afirst bulk fluid;

(C) after the step of wetting, introducing a second bulk fluid into thechamber, wherein the second bulk fluid comprises a second liquid phase,and wherein the second liquid phase is immiscible with the first liquidphase;

(D) applying a second shear between the second bulk fluid in the chamberand at least the first surface; and

(E) making an electrical impedance spectroscopy measurement between thefirst and second electrode.

According to another preferred embodiment of this method, it includesthe steps of: before the step of applying the shear, making a firstelectrical impedance spectroscopy measurement between the first andsecond electrode; during or after the step of applying the shear, makinga second electrical impedance spectroscopy measurement between the firstand second electrode; comparing the first electrical impedancespectroscopy measurement to the second electrical impedance spectroscopymeasurement; and based on the step of comparing, inferring any changesin the wetting of the first surface. Preferably, the step of inferringcomprises assuming an equivalent electrical circuit model to matchexperimental impedance changes using non-linear regression techniques.

According to a presently most preferred embodiment, the step of takingan electrical impedance spectroscopy measurement includes: operativelyconnecting an alternating electrical potential source between the firstand second electrodes; while operatively connected to the first andsecond electrodes, varying the electrical potential or the frequency ofthe alternating electrical potential source; and while varying theelectrical potential or the frequency of the alternating electricalpotential source, measuring electrical impedance between the firstelectrode and second electrode to obtain an electrical impedancespectroscopy measurement.

According to yet another embodiment of this method, the methodadditionally includes the step of: designing a composition of a firstwell fluid or conditions of introducing the first well fluid into a wellto achieve a change in wetting of a downhole surface in the well.

According to a further embodiment of the above method, the methodadditionally includes the step of: introducing the first well fluid intothe well, wherein the well fluid and conditions of introducing aredesigned to achieve the desired change in wetting of a downhole surfacein the well.

According to a further embodiment of the above method, the methodadditionally includes the step of: after introducing the first wellfluid into the well, introducing a second well fluid into the well toreach the downhole surface in the well.

According to an embodiment, the apparatus of the method includes areference electrode and the method includes the step of operativelyconnecting the alternating electrical potential source to the referenceelectrode.

In an embodiment, the chamber is cylindrical. In another embodiment, thefirst surface is curved. Preferably, the geometry of the chamber and thefirst surface simulate the geometry of a surface in a well.

In an embodiment, the first surface is oil-wettable. In anotherembodiment, the first surface is water-wettable. The first surface canbe both oil-wettable and water-wettable, such that wetting with oneblocks the surface wettability to another.

In an embodiment, the first surface is of the first electrode and thefirst electrode is selected to be the same material as a metallictubular used in a well.

In another embodiment, the first surface is of the first dielectricsolid material, and wherein the first dielectric solid materialcomprises a filter cake, a polymeric material, or any combinationthereof. In yet another embodiment, the first surface is of the firstdielectric solid material and the first dielectric solid materialcomprises a rock material. The rock material can be or comprise asedimentary rock. Preferably, the rock material is selected to simulatea downhole subterranean formation in a well. In such an embodiment, therock can be saturated with the first liquid phase fluid. This could beused, for example, to simulate a rock surface in a well that is wettedwith such a liquid phase.

It should be understood that a material of the first surface can bedifferent than a material of the second surface. For example, the firstsurface can be of the first dielectric solid material and the secondsurface can be of the second electrode. It should also be understoodthat a material of the first surface can be the same as a material ofthe second surface. In another embodiment, the second surface is of thesecond dielectric solid material and the second dielectric solidmaterial is the same material as the first dielectric solid material.

In an embodiment, the step of wetting with the first liquid phaseincludes: (i) introducing a first bulk fluid into the chamber, whereinthe first bulk fluid comprises the first liquid phase; and (ii) applyinga first shear between the first fluid in the chamber and at least thefirst surface.

According to an embodiment, the first liquid phase is a dielectric.According to another embodiment, the first liquid phase is oleaginous.For example, the first liquid phase can be the oil of an oil-baseddrilling mud used in a well.

According to an embodiment, the second liquid phase has a dielectricconstant at least 10% different from the dielectric constant of thefirst liquid phase.

According to an embodiment, the second liquid phase includes water. Inthis embodiment, the second liquid phase preferably includes anelectrolyte. In an embodiment, the second liquid phase is the continuousphase of the second bulk fluid. In yet another embodiment, the secondbulk fluid can be an emulsion of the first liquid phase and the secondliquid phase. For example, the second bulk fluid can be an oil-in-wateremulsion.

In an embodiment, the second bulk fluid includes various othercomponents. For example, in a preferred embodiment, the second bulkfluid includes a surfactant. In an embodiment, the second bulk fluid caninclude a solid particulate. The solid particulate can help remove aprior film on the first surface by abrasive action during shearingbetween the first surface and the second bulk fluid. In anotherembodiment, the second bulk fluid includes a chemical leaching agent forattacking the first dielectric solid material. In yet anotherembodiment, the second bulk fluid is a foam. For example, the bulk fluidcan be foamed or energized with nitrogen gas.

It should be understood that well fluids to be simulated according tothe methods of the invention can have widely ranging bulk density. Forexample, in an embodiment the second bulk fluid can have a bulk densityanywhere in the range of 4 ppg to 25 ppg.

In an embodiment, the second bulk fluid is a spacer fluid for use in awell. The composition of the second bulk fluid can be changed duringshear to simulate fingering, mixing, or channeling during theintroducing of such a well fluid into a well.

In an embodiment of the methods, the change in voltage of thealternating electric potential source is in a pseudolinear range. Itshould be understood that a pseudolinear range means that if V₁ gives I₁and V₂ gives I₂, then V₁+V₂ should give I₁+I₂.

In an embodiment of the methods, the change in frequency of thealternating electric potential source is anywhere in the range of 1microHertz to 1 gigaHertz.

In yet another embodiment of the methods, the current measured fordetermining electrical impedance has the same frequency as thealternating electric potential source but a shifted phase.

In an application of the methods, the second bulk fluid can be testedfor the design shear and design time for a well fluid in a well, such asfor a spacer fluid.

In an embodiment, the methods additionally include the step of:controlling the temperature of the second bulk fluid in the chamber. Forexample, the step of controlling the temperature of the second bulkfluid in the chamber can include controlling the temperature to be thedesign temperature for a well fluid in a well. It should be understoodthat controlling the temperature can include heating the fluid while inthe chamber.

In an embodiment, the methods can additionally include the step of:controlling the pressure of the second bulk fluid in the chamber. Forexample, the step of controlling the pressure of the second bulk fluidin the chamber can include controlling the pressure to be the designpressure for a well fluid in a well. It should be understood thatcontrolling the pressure can include pressurizing the fluid while in thechamber.

In an embodiment, the step of inferring comprises assuming an equivalentelectrical circuit model for the first electrical impedance spectroscopyand second electrical impedance spectroscopy to match experimentalimpedance changes using non-linear regression techniques.

Preferably, the wetting of first surface is determined as a percentageof the surface that is water-wetted or oil-wetted. For example, thewetting of the first surface in the bulk fluid is determined as apercentage of the first surface that is water wet at: (a) the beginningof the contact time at the contact shear of the bulk fluid; and (b) theend of the contact time at the contact shear of the bulk fluid.

According to an embodiment, the design conditions of introducing thefirst well fluid into the well include any one of the following: designvolume, design shear, design temperature, design pressure, and designpumping time.

In an embodiment, the test fluid is a water-based fluid. For example,the test fluid can be an oil-in-water emulsion. In an embodiment, theoil-in-water emulsion simulates a downhole fluid that results from themixing of a prior oil-based drilling mud with a spacer fluid that is forchanging the wetting of downhole tubular surfaces from oil-wetted towater-wetted before cementing.

In an embodiment where the test material is selected for being similarin substance to a substance of a solid surface in a well, the test fluidis selected for having the design composition of a downhole fluid to becontacted with the solid surface in the well. For example, the downholefluid is a water-based fluid, such as an oil-in-water emulsion. In someapplications, the downhole fluid is a water-in-oil emulsion.

In a preferred embodiment, the system is tested under similar designconditions as the solid surface in the well and the downhole fluid,including at least the design conditions of temperature, fluid contactshear, and fluid contact time at the fluid contact shear. Where thesystem of the test material and the test fluid is tested under similardownhole conditions as the solid surface in the well and the downholefluid, the method preferably additionally includes at least the designcondition of fluid contact pressure. In an embodiment, the wettabilityor wetting of the test material in the test fluid is determined as apercentage of the surface that is water-wetted or oil-wetted. Otherparameters can additionally be simulated, such as well fluid volume anddownhole mixing with another fluid. Preferably, the wetting of the testmaterial in the test fluid is determined as a percentage of the surfacethat is water wet or oil wet at: (a) the beginning of the fluid contacttime at the fluid contact shear; and (b) the end of the fluid contacttime at the fluid contact shear.

In an additional embodiment, wetting of the test material is compared atintermediate fluid compositions made with predetermined concentrationsof a first oil based fluid, a second water based fluidspacer/wash/inverter-fluid/lead cement slurry with the “control wetting”of the surfaces with the pure second water based fluid. It can beappreciated that the first fluid may be water based and the second fluidmay be oil based as the situation demands during the well operations.

In another additional embodiment, the efficiency of the erosion orremoval of the coating generated by a first fluid by the second fluidcan be measured at predetermined intermediate concentrations of thefirst fluid and the second fluid under controlled hydrodynamicconditions under the influence of pressure and temperature. Theelectrical properties associated with this process are recordeddynamically to compare with the control properties with no coating inplace and just the second fluid in the system.

The focus of the technique is to understand the contact time and shearrate requirements under pressure and temperature for approaching thewetting values of the test material in contact with the control purefluid that is deployed for the cleanout operation under pressure andtemperature. Wettability or wetting are surface characteristics and maybe related to impedance, double layer capacitance, polarizationresistance, or charge transfer resistance as accordingly modeled by arelevant equivalent electrical circuit.

In another embodiment, the method can additionally include the step ofadjusting or optimizing the design composition of the downhole fluid tobe contacted with the solid surface in the well based on the wettabilityor wetting of the test material in the test fluid.

In an embodiment, the method can further include a step of introducing awell fluid into the well, wherein the well fluid and conditions ofintroducing are adapted to achieve a downhole fluid and conditions ofcontacting the solid surface in the well to achieve a design wettabilityor wetting of the solid surface in the well.

CONCLUSION

Bulk conductivity information alone is insufficient to determine surfacewettability or wetting.

Contact angle measurements are not feasible to be carried out withparticulate-laden fluids. Moreover, contact angle measurement is ananalytical technique that needs sophisticated tensiometers orgoniometers.

Visual techniques like imaging to measure contact angle have beenattempted but are not easily made quantitative.

The dye method demonstrated qualitative changes in surface wetting.Attempts were made to quantify using an imaging technique. However,curved surfaces could not be analyzed using this method. Repeatabilitycould not be confirmed on curved surfaces because of high errors inimaging and image processing techniques and interpretation. Thistechnique is not in-situ as the tested surface needed to be taken out ofthe solution to take photographs.

The disclosed invention provides an opportunity to carry outmeasurements using a non-invasive technique and quantify water- oroil-wettability or wetting at in-situ conditions. With continuousinjection of surfactants and homogenization in the cell, using a mixingpaddle, capacitances, and resistances can be monitored with respect to acontrol fluid to confirm the desired water wettability or wetting.

The methods can be used in surfactant package optimization to renderwater wet surfaces at downhole conditions.

In some applications, the methods can be used to provide increasedprobability of achieving full cement shear bond strength and bettercorrelation with cement bond logs.

Prior lab testing using this technique and job execution in the field asdesigned can decrease the probability of micro annulus development andloss of interfacial bond during the lifecycle of the well and henceimproves long-term zonal isolation.

This process can be carried out at HPHT by varying the type of formationor tubular surface experienced downhole, varying surface roughness, millvarnished, polished, corroded, etc.

Therefore, the present invention is well adapted to attain the ends andadvantages mentioned as well as those that are inherent therein.

The particular embodiments disclosed above are illustrative only, as thepresent invention may be modified and practiced in different butequivalent manners apparent to those skilled in the art having thebenefit of the teachings herein. It is, therefore, evident that theparticular illustrative embodiments disclosed above may be altered ormodified and all such variations are considered within the scope andspirit of the present invention.

The various elements or steps according to the disclosed elements orsteps can be combined advantageously or practiced together in variouscombinations or sub-combinations of elements or sequences of steps toincrease the efficiency and benefits that can be obtained from theinvention.

The invention illustratively disclosed herein suitably may be practicedin the absence of any element or step that is not specifically disclosedor claimed.

Furthermore, no limitations are intended to the details of construction,composition, design, or steps herein shown, other than as described inthe claims.

What is claimed is:
 1. A method comprising the steps of: (A) obtainingor providing an apparatus comprising: (i) a container forming a chamber;(ii) a first surface exposed to or in the chamber, wherein the firstsurface is of a first electrode; (iii) a second surface exposed to or inthe chamber, wherein the second surface is of a second electrode;wherein the first surface is electrically insulated from the secondsurface; (B) wetting at least the first surface with a first liquidphase of a first bulk fluid; (C) after the step of wetting, introducinga second bulk fluid into the chamber, wherein the second bulk fluidcomprises a second liquid phase, and wherein the second liquid phase isimmiscible with the first liquid phase; (D) applying a shear between thesecond bulk fluid in the chamber and at least the first surface; and (E)at least once during or after applying the shear, making an electricalimpedance spectroscopy measurement between the first and secondelectrode.
 2. The method according to claim 1, additionally comprisingthe steps of: before the step of applying the shear, making a firstelectrical impedance spectroscopy measurement between the first andsecond electrode; during or after the step of applying the shear, makinga second electrical impedance spectroscopy measurement between the firstand second electrode; comparing the first electrical impedancespectroscopy measurement to the second electrical impedance spectroscopymeasurement; and based on the step of comparing, inferring any changesin the wetting of the first surface.
 3. The method according to claim 1,wherein the first surface is curved.
 4. The method according to claim 1,wherein the step of wetting comprises: (i) introducing the first bulkfluid into the chamber; and (ii) applying a first shear between thefirst fluid in the chamber and at least the first surface.
 5. The methodaccording to claim 1, wherein the first liquid phase is oleaginous. 6.The method according to claim 1, wherein the second bulk fluid comprisesany mixture of the first bulk fluid and the second liquid phase.
 7. Themethod according to claim 1, wherein the second liquid phase compriseswater.
 8. The method according to claim 7, wherein the second liquidphase comprises an electrolyte.
 9. The method according to claim 1,wherein the second bulk fluid comprises a surfactant.
 10. The methodaccording to claim 1, wherein the second bulk fluid comprises a solidparticulate.
 11. The method according to claim 1, wherein the secondbulk fluid is a foam.
 12. The method according to claim 1, wherein thecomposition of the second bulk fluid is changed during the step ofapplying shear.
 13. The method according to claim 1, wherein the secondbulk fluid is tested at the design shear and design time for a spacerfluid in a portion of a well.
 14. The method according to claim 1,additionally comprising the step of: controlling the temperature of thesecond bulk fluid in the chamber, wherein the step of controlling thetemperature of the second bulk fluid in the chamber comprisescontrolling the temperature to be the design temperature for a wellfluid in a well.
 15. The method according to claim 1, additionallycomprising the step of: controlling the pressure of the second bulkfluid in the chamber, wherein the step of controlling the pressure ofthe second bulk fluid in the chamber comprises controlling the pressureto be the design pressure for a well fluid in a well.
 16. The methodaccording to claim 2, additionally comprising the steps of: comparingthe first electrical impedance spectroscopy measurement to the secondelectrical impedance spectroscopy measurement; and based on the step ofcomparing, inferring any changes in the wetting of the first surface.17. The method according to claim 16, wherein the step of inferringcomprises assuming an equivalent electrical circuit model for the firstelectrical impedance spectroscopy measurement and second electricalimpedance spectroscopy measurement to match experimental impedancechanges using non-linear regression techniques.
 18. The method accordingto claim 16, additionally comprising the step of: designing acomposition of a first well fluid or conditions of introducing the firstwell fluid into a well to achieve a change in wetting of a downholesurface in the well.
 19. The method according to claim 18, additionallycomprising the step of: introducing the first well fluid into the well,wherein the well fluid and conditions of introducing are designed toachieve the desired change in wetting of a downhole surface in the well.20. The method according to claim 19, additionally comprising the stepof: after introducing the first well fluid into the well, introducing asecond well fluid into the well to reach the downhole surface in thewell.
 21. The method according to claim 20, wherein the second wellfluid is a cement composition.
 22. A method comprising the steps of: (A)positioning a first electrode and a second electrode in an annulusbetween a metallic tubular and the borehole of a wellbore in a well; (B)pumping a fluid through though the annulus and between the firstelectrode and the second electrode; and (C) at least once during orafter the step of pumping, making an electrical impedance spectroscopymeasurement between the first and second electrode.
 23. An apparatuscomprising: (A) a container forming a chamber; (B) a first surfaceexposed to or in the chamber, wherein the first surface is of a firstelectrode; (C) a second surface exposed to or in the chamber, whereinthe second surface is of a second electrode, and wherein the firstsurface is electrically insulated from the second surface; (D) a firstliquid phase wetted on at least the first surface; (E) a bulk fluid inthe chamber, wherein the bulk fluid comprises a second liquid phase, andwherein the second liquid phase is immiscible with the first liquidphase; (F) a means for controlling the shear rate between the bulk fluidin the chamber and at least the first surface; (G) an alternatingelectrical potential source operatively connected between the first andsecond electrodes; (H) means for controlling the electrical potential orthe frequency of the alternating electrical potential source; and (I)means for measuring changes in electrical impedance between the firstelectrode and second electrode; whereby electrical impedancespectroscopy measurements can be made between the first electrode andthe second electrode before, during, or after controlling the shearrate.